Pesticidal agents on the basis of 1-aryl-aminopyrrol

ABSTRACT

Pesticidal Compounds The invention relates to 1-aryl-5-disubstituted-aminopyrrole derivatives of formula (I) or salts thereof: wherein the various symbols are as defined in the description, to processes for their preparation, to compositions thereof, and to their use for the control of pests (including arthropods and helminths).

The invention relates to novel 1-aryl-5-disubstituted-aminopyrrolederivatives, processes for their preparation, to compositions thereof,and to their use for the control of pests (including arthropods andhelminths).

The control of insects, arachnids and helminths with 1-arylpyrrolecompounds has been described in patent publication numbers EP 0372982and EP 0460940.

However, since modern pesticides must meet a wide range of demands, forexample regarding level, duration and spectrum of action, use spectrum,toxicity, combination with other active substances, combination withformulation auxiliaries or synthesis, and since the occurrence ofresistances is possible, the development of such substances can never beregarded as concluded, and there is constantly a high demand for novelcompounds which are advantageous over the known compounds, at least asfar as some aspects are concerned.

It is an object of the present invention to provide new pesticides whichmay be used in domestic companion animals.

It is advantageous to apply pesticides to animals in oral form so as toprevent the possible contamination of humans or the surroundingenvironment.

Another object of the invention is to provide new pesticides which maybe used in lower dose than existing pesticides.

Another object of the invention is to provide new pesticides which aresubstantially non-emetic.

Another object of the invention is to provide new pesticides which aresafer to the user and the environment.

Another object of the invention is to provide new pesticides whichprovide effective pest control over an extended period with a singleoral application.

These objects are met in whole or in part by the present invention.

The present invention provides a compound which is a1-aryl-5-disubstituted-aminopyrrole derivative of formula (I):

wherein:

Q is CN or CSNH₂;

R¹ is CN, CF₃ or CSNH₂;

R² is (C₁-C₃)-alkyl or (C₁-C₃)-haloalkyl;

R³ is (C₃-C₆)-alkenyl, (C₃-C₆)-alkynyl, R⁶, (C₃-C₆)-cycloalkyl or(C₁-C₄)-alkyl which last mentioned group is unsubstituted or substitutedby one or more radicals selected from the group consisting of halogen,(C₁-C₄)-alkoxy, S(O)_(m)R⁷, R⁶, (C₃-C₆)-cycloalkyl, CO₂(CH₂)_(q)R⁶,CO₂(CH₂)_(q)R^(6a) and CO₂R⁷;

R⁴ is (C₂-C₄)-alkyl or (C₂-C₄)-haloalkyl which groups are unsubstitutedor substituted by a radical selected from the group consisting ofNHCOR⁸, NHR⁸, NR⁸COR⁸, OCOR⁸, OR⁶, OR^(6a), S(O)_(p)(CH₂)_(q)R⁶,S(O)_(p)(CH₂)_(q)R^(6a), ═N—R⁸, ═NNHR⁸, ═NOR⁸, ═NOH, ═NNHC(═X)R⁸,═NNHC(═X)NH₂, ═NNR⁸C(═X)NH₂, ═NNHC(═O)O(CH₂)_(q)R⁹, (C₁-C₄)-alkoxy andS(O)_(m)R⁷ (wherein two (C₁-C₄)-alkoxy or S(O)_(m)R⁷ radicals may beattached to the same carbon atom to form an acetal, thioacetal orhemithioacetal group or a cyclic acetal, thioacetal or hemithioacetalwhich contains 5 or 6 ring atoms); or is CO₂R⁹, COCOR¹⁰, SO₂R⁸, COR⁸,COCH₂OR⁸ or P(═X)(—YR⁸)(-ZR^(8a));

R⁵ is CF₃, OCF₃, SF₅ or halogen;

W is C-halogen, C—NR¹¹R¹² or N;

X is O or S;

Y and Z are each independently O, S or a covalent bond;

R⁶ is phenyl unsubstituted or substituted by one or more radicalsselected from the group consisting of halogen, (C₁-C₄)-alkyl,(C₁-C₄)-haloalkyl, (C₁-C₄)-alkoxy, (C₁-C₄)-haloalkoxy, CN, NO₂,S(O)_(p)R⁷ and NR¹¹R¹²;

R^(6a) is heteroaryl unsubstituted or substituted by one or moreradicals selected from the group consisting of halogen, (C₁-C₄)-alkyl,(C₁-C₄)-haloalkyl, (C₁-C₄)-alkoxy, (C₁-C₄)-haloalkoxy, CN, NO₂,S(O)_(p)R⁷, NR¹¹R¹², OH and oxo;

R⁷ is (C₁-C₄)-alkyl or (C₁-C₄)-haloalkyl;

R⁸ and R^(8a) are each independently (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl,(C₃-C₆)-cycloalkyl-(C₁-C₃)-alkyl or (CH₂)_(q)R⁶;

R⁹ is R⁶, (C₃-C₄)-alkenyl, (C₃-C₄)-alkynyl or (C₁-C₄)-alkyl which lastmentioned group is unsubstituted or substituted by one or more radicalsselected from the group consisting of halogen, (C₁-C₄)-alkoxy,(C₁-C₄)-haloalkoxy, R⁶, S(O)_(m)R⁶ and (C₃-C₆)-cycloalkyl;

R¹⁰ is OR⁹ or NR¹³R¹⁴;

R¹¹ and R¹² are each independently H, (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl,(C₃-C₄)-alkenyl, (C₃-C₄)-haloalkenyl, (C₃-C₄)-alkynyl,(C₃-C₆)-cycloalkyl or (C₃-C₆)-cycloalkyl-(C₁-C₄)-alkyl; or

R¹¹ and R¹² together with the attached N atom form a five- orsix-membered saturated or unsaturated ring which optionally contains anadditional hetero atom in the ring which is selected from O, S and N,the ring being unsubstituted or substituted by one or more radicalsselected from the group consisting of halogen, (C₁-C₄)-alkyl and(C₁-C₄)-haloalkyl;

R¹³ is H, (C₁-C₄)-alkyl or R⁶;

R¹⁴ is H or R⁹;

m, n and p are each independently 0, 1, or 2;

q is 0 or 1; and

each heteroaryl in the above-mentioned radicals is independently aheteroaromatic radical having 3 to 7 ring atoms and 1, 2 or 3 heteroatoms in the ring selected from the group consisting of N, O and S;

or a pesticidally acceptable salt thereof.

These compounds possess valuable pesticidal properties.

The invention also encompasses any stereoisomer, enantiomer or geometricisomer, and mixtures thereof.

By the term “pesticidally acceptable salts” is meant salts the anions ofwhich are known and accepted in the art for the formation of salts forpesticidal use.

Suitable acid addition salts, e.g. formed by compounds of formula (I)containing an amino group, include salts with inorganic acids, forexample hydrochlorides, sulphates, phosphates and nitrates and saltswith organic acids for example acetic acid.

In the present specification, including the accompanying claims, theaforementioned substituents have the following meanings:

Halogen atom means fluorine, chlorine, bromine or iodine.

The term “halo” before the name of a radical means that this radical ispartially or completely halogenated, that is to say, substituted by F,Cl, Br, or I, in any combination, preferably by F or Cl.

Alkyl groups and portions thereof (unless otherwise defined) may bestraight- or branched-chain.

The expression “(C₁-C₄)-alkyl” is to be understood as meaning anunbranched or branched hydrocarbon radical having 1, 2, 3 or 4 carbonatoms, such as, for example a methyl, ethyl, propyl, isopropyl, 1-butyl,2-butyl, 2-methylpropyl or tert-butyl radical.

Alkyl radicals and also in composite groups, unless otherwise defined,preferably have 1 to 4 carbon atoms.

“(C₁-C₄)Haloalkyl” means an alkyl group mentioned under the expression“(C₁-C₄)alkyl” in which one or more hydrogen atoms are replaced by thesame number of identical or different halogen atoms, such asmonohaloalkyl, perhaloalkyl, CF₃, CHF₂, CH₂F, CHFCH₃, CF₃CH₂, CF₃CF₂,CHF₂CF₂, CH₂FCHCl, CH₂Cl, CCl₃, CHCl₂ or CH₂CH₂Cl.

“(C₁-C₄)Alkoxy” means an alkoxy group whose carbon chain has the meaninggiven under the expression “(C₁-C₆)alkyl”. “Haloalkoxy” is, for example,OCF₃, OCHF₂, OCH₂F, CF₃CF₂O, OCH₂CF₃ or OCH₂CH₂Cl.

“(C₂-C₄)Alkenyl” means an unbranched or branched non-cyclic carbon chainhaving a number of carbon atoms which corresponds to this stated rangeand which contains at least one double bond which can be located in anyposition of the respective unsaturated radical. “(C₂-C₄)Alkenyl”accordingly denotes, for example, the vinyl, allyl, 2-methyl-2-propenylor 2-butenyl.

“(C₃-C₄)Alkynyl” means an unbranched or branched non-cyclic carbon chainhaving a number of carbon atoms which corresponds to this stated rangeand which contains one triple bond which can be located in any positionof the respective unsaturated radical. “(C₃-C₄)Alkynyl” accordinglydenotes, for example, the propargyl, 1-methyl-2-propynyl, 2-butynyl or3-butynyl group.

Cycloalkyl groups preferably have from three to seven carbon atoms inthe ring and are optionally substituted by halogen or alkyl.

“(C₃-C₆)-Cycloalkyl-(C₁-C₄)-alkyl” means a (C₁-C₄)-alkyl group which issubstituted by a (C₃-C₆)-cycloalkyl ring.

In compounds of formula (I) the following examples of radicals areprovided:

An example of alkyl substituted by cycloalkyl is cyclopropylmethyl;

an example of alkyl substituted by alkoxy is methoxymethyl (CH₂OCH₃);and

an example of alkyl substituted by alkylthio is methylthiomethyl(CH₂SCH₃).

“Heteroaryl” means a heteroaromatic ring which preferably contains oneor more, in particular 1, 2 or 3, hetero atoms in the heteroaryl ring,preferably selected from the group consisting of N, O and S; it haspreferably preferably 5 to 7 ring atoms. The heteroaryl radical is forexample, a mono-, bi- or polycyclic aromatic system in which at least 1ring contains one or more hetero atoms, for example pyridyl,pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, thienyl, thiazolyl,thiadiazolyl, oxazolyl, isoxazolyl, furyl, pyrrolyl, pyrazolyl,imidazolyl and triazolyl.

The term pests means arthropod pests (including insects and arachnids),and helminths (including nematodes).

In the following preferred definitions it is generally to be understoodthat where symbols are not specifically defined they are to be aspreviously defined in the description.

Preferably Q and R¹ are each CN.

Preferably W is C—Cl or N (more preferably W is C—Cl).

Preferably R² is CF₃, CF₂Cl or CFCl₂ (more preferably R² is CF₃);

Preferably R³ is (C₁-C₄)-alkyl unsubstituted or substituted by one ormore radicals selected from the group consisting of halogen,(C₁-C₄)-alkoxy, S(O)_(m)R⁷, R⁶, (C₃-C₆)-cycloalkyl, CO₂(CH₂)_(q)R⁶ andCO₂R⁷ (more preferably R³ is (C₁-C₄)-alkyl unsubstituted or substitutedby one or more radicals selected from the group consisting of halogen,(C₁-C₄)-alkoxy and S(O)_(m)R⁷.

Preferably R⁴ is (C₂-C₄)-alkyl or (C₂-C₄)-haloalkyl which groups areunsubstituted or substituted by a radical selected from the groupconsisting of S(O)_(p)(CH₂)_(q)R⁶, S(O)_(p)(CH₂)_(q)R^(6a), ═N—R⁸,═NNHR⁸, ═NOR, ═NNHC(═X)R⁸, ═NNHC(═X)NH₂, ═NNHC(═O)O(CH₂)_(q)R⁹,(C₁-C₄)-alkoxy and S(O)_(m)R⁷ (wherein two (C₁-C₄)-alkoxy or S(O)_(m)R⁷radicals may be attached to the same carbon atom to form an acetal,thioacetal or hemithioacetal group or a cyclic acetal, thioacetal orhemithioacetal which contains 5 or 6 ring atoms); (more preferably R⁴ is(C₂-C₄)-alkyl or (C₂-C₄)-haloalkyl which groups are unsubstituted orsubstituted by a radical selected from the group consisting of(C₁-C₄)-alkoxy and S(O)_(m)R⁷ (wherein two (C₁-C₄)-alkoxy or S(O)_(m)R⁷radicals may be attached to the same carbon atom to form an acetal,thioacetal or hemithioacetal group or a cyclic acetal, thioacetal orhemithioacetal which contains 5 or 6 ring atoms)).

Preferably R⁵ is CF₃ or OCF₃ (more preferably R³ is CF₃).

A preferred class of compounds of formula (I) are those in which:

Q and R¹ are each CN;

R² is CF₃, CF₂Cl or CFCl₂ (more preferably R² is CF₃);

R⁵ is CF₃;

W is C—Cl; and

the other radicals are as defined in claim 1.

A further preferred class of compounds of formula (I) are those inwhich:

Q and R¹ are each CN;

R² is CF₃, CF₂Cl or CFCl₂ (more preferably R² is CF₃);

R⁴ is (C₂-C₄)-alkyl or (C₂-C₄)-haloalkyl which groups are substituted bya radical selected from the group consisting of NHCOR⁸, NHR⁸, NR⁸COR⁸,OCOR⁸, OR⁶, OR^(6a), S(O)_(p)(CH₂)_(q)R⁶, S(O)_(p)(CH₂)_(q)R^(6a),═N—R⁸, ═NNHR⁸, ═NOR⁸, ═NOH, ═NNHC(═X)R⁸, ═NNHC(═X)NH₂, ═NNR⁸C(═X)NH₂,═NNR⁸C(═X)NH₂, ═NNHC(═O)O(CH₂)_(q)R⁹, (C₁-C₄)-alkoxy and S(O)_(m)R⁷(wherein two (C₁-C₄)-alkoxy or S(O)_(m)R⁷ radicals may be attached tothe same carbon atom to form an acetal, thioacetal or hemithioacetalgroup or a cyclic acetal, thioacetal or hemithioacetal which contains 5or 6 ring atoms); or is CO₂R⁹, COCOR¹⁰, SO₂R⁸, COR⁸, COCH₂OR⁸ orP(═X)(—YR⁸)(-ZR^(8a));

R⁵ is CF₃;

W is C—Cl; and

the other radicals are as defined in claim 1.

A further preferred class of compounds of formula (I) are those inwhich:

Q and R¹ are each CN,

R² is CF₃;

R³ is (C₁-C₄)-alkyl unsubstituted or substituted by one or more radicalsselected from the group consisting of halogen, (C₁-C₄)-alkoxy,S(O)_(m)R⁷, R⁶, (C₃-C₆)-cycloalkyl, CO₂(CH₂)_(q)R⁶ and CO₂R⁷;

R⁴ is (C₂-C₄)-alkyl or (C₂-C₄)-haloalkyl which groups are substituted bya radical selected from the group consisting of S(O)_(p)(CH₂)_(q)R⁶,S(O)_(p)(CH₂)_(q)R^(6a), ═N—R⁸, ═NNHR₃, ═NOR⁸, ═NNHC(═X)R⁸,═NNHC(═X)NH₂, ═NNHC(═O)O(CH₂)_(q)R⁹, (C₁-C₄)-alkoxy and S(O)_(m)R⁷(wherein two (C₁-C₄)-alkoxy or S(O)_(m)R⁷ radicals may be attached tothe same carbon atom to form an acetal, thioacetal or hemithioacetalgroup or a cyclic acetal, thioacetal or hemithioacetal which contains 5or 6 ring atoms); or is CO₂R⁹ or COCH₂OR⁸;

R⁵ is CF₃;

W is C—Cl; and

the other radicals are as defined in claim 1.

A further preferred class of compounds of formula (I) are those wherein:

Q and R¹ are each CN;

R² is CF₃;

R³ is (C₁-C₄)-alkyl;

R⁴ is (C₂-C₄)-alkyl or (C₂-C₄)-haloalkyl which groups are substituted bya radical selected from the group consisting of S(O)_(p)(CH₂)_(q)R⁶,S(O)_(p)(CH₂)_(q)R^(6a), ═N—R⁸, ═NNHR⁸, ═NOR⁸, ═NNHC(═X)R⁸,═NNHC(═X)NH₂, ═NNHC(═O)O(CH₂)_(q)R⁹, (C₁-C₄)-alkoxy and S(O)_(m)R⁷(wherein two (C₁-C₄)-alkoxy or S(O)_(m)R⁷ radicals may be attached tothe same carbon atom to form an acetal, thioacetal or hemithioacetalgroup or a cyclic acetal, thioacetal or hemithioacetal which contains 5or 6 ring atoms); or is CO₂R⁹ or COCH₂OR⁸;

R⁵ is CF₃;

W is C—Cl; and

the other radicals are as defined in claim 1.

A further preferred class of compounds of formula (I) are those wherein:

Q and R¹ are each CN;

W is C—Cl, C—NR¹¹R¹² or N (more preferably W is C—Cl);

R² and R⁵ are each CF₃;

R³ is (C₁-C₄)-alkyl (more preferably R³ is CH₃);

R⁴ is (C₂-C₃)-alkyl substituted by a radical selected from the groupconsisting of ═NOR⁸ (wherein R⁸ is (C₁-C₄)-alkyl or(C₃-C₆)-cycloalkyl-(C₁-C₃)-alkyl), ═NNHC(═O)R⁸ (wherein R⁸ is(C₁-C₄)-alkyl or R⁶), ═NNHC(═S)NH₂, (C₁-C₄)-alkoxy and S(O)_(m)R⁷(wherein two (C₁-C₄)-alkoxy or S(O)_(m)R⁷ radicals may be attached tothe same carbon atom to form an acetal or thioacetal group or a cyclicacetal or thioacetal which contains 5 ring atoms); or is CO₂R⁹ orCOCH₂OR⁸ (wherein R⁸ is (C₁-C₄)-alkyl);

R⁷ is (C₁-C₄)-alkyl;

R⁹ is (C₁-C₄)-alkyl substituted by R⁶, and

R¹¹ and R¹² are each independently (C₁-C₄)-alkyl.

A further preferred class of compounds of formula (I) are those wherein:

Q and R¹ are each CN;

W is C—Cl;

R² and R⁵ are each CF₃;

R³ is (C₁-C₄)-alkyl substituted by (C₃-C₆)-cycloalkyl;

R⁴ is (C₂-C₃)-alkyl substituted by a radical selected from the groupconsisting of ═NOR⁸ (wherein R⁸ is (C₁-C₄)-alkyl or(C₃-C₆)-cycloalkyl-(C₁-C₃)-alkyl), ═NNHC(═O)R⁸ (wherein R⁸ is(C₁-C₄)-alkyl or R⁶), ═NNHC(═S)NH₂, (C₁-C₄)-alkoxy and S(O)_(m)R⁷(wherein two (C₁-C₄)-alkoxy or S(O)_(m)R⁷ radicals may be attached tothe same carbon atom to form an acetal or thioacetal group or a cyclicacetal or thioacetal which contains 5 ring atoms); or is CO₂R⁹ orCOCH₂OR⁸ (wherein R⁸ is (C₁-C₄)-alkyl);

R⁷ is (C₁-C₄)-alkyl;

R⁹ is (C₁-C₄)-alkyl substituted by R⁶, and

R¹¹ and R¹² are each independently (C₁-C₄)-alkyl.

The compounds of general formula (I) can be prepared by the applicationor adaptation of known methods (i.e. methods heretofore used ordescribed in the chemical literature.

In the following description of processes when symbols appearing informulae are not specifically defined, it is understood that they are“as defined above” in accordance with the first definition of eachsymbol in the specification.

According to a further feature of the invention compounds of formula (I)wherein Q is CN, R¹ is CN or CF₃, and R², R³, R⁴, R⁵, W and n are asdefined above, may be prepared by the reaction of a correspondingcompound of formula (II):

wherein the various values are as defined above, with a compound offormula (III):R⁴-L   (III)

wherein R⁴is as defined above, and L is a leaving group.

For alkylations, where R⁴ is (C₂-C₄)-alkyl or (C₂-C₄)-haloalkyl whichgroups are unsubstituted or substituted by a radical selected from thegroup consisting of NHCOR⁸, NHR⁸, NR⁸COR⁸, OCOR⁸, OR⁶, OR^(6a),S(O)_(p)(CH₂)_(q)R⁶, S(O)_(p)(CH₂)_(q)R^(6a), (C₁-C₄)-alkoxy andS(O)_(m)R⁷ (wherein two (C₁-C₄)-alkoxy or S(O)_(m)R⁷ radicals may beattached to the same carbon atom to form an acetal, thioacetal orhemithioacetal group or a cyclic acetal, thioacetal or hemithioacetalwhich contains 5 or 6 ring atoms), L is preferably halogen,alkylsulfonyloxy or arylsulfonyloxy (more preferably chlorine, bromine,iodine, methylsulfonyloxy or p-toluenesulfonyloxy). A base is optionallypresent in the reaction which is generally performed in an inert solventsuch as tetrahydrofuran, dioxan, acetonitrile, toluene, diethyl ether,dichloromethane, dimethylsulfoxide or N,N-dimethylformamide, at atemperature of from −30° C. to 200° C., preferably at 20° C. to 100° C.The base is generally an alkali metal hydroxide such as potassiumhydroxide, an alkali metal hydride such as sodium hydride, an alkalimetal carbonate such as potassium carbonate or sodium carbonate, analkali metal alkoxide such as sodium methoxide, an alkaline earth metalcarbonate such as calcium carbonate, or an organic base such as atertiary amine, for example triethylamine or ethyldiisopropylamine, orpyridine, or 1,8-diazabicyclo[5.4.0]undec-7-en (DBU).

For acylations, where R⁴ is CO₂R⁹, COCOR¹⁰, COR⁸ or COCH₂OR⁸, (III) ispreferably an acid halide where L is preferably chlorine or bromine(more preferably chlorine). A base is optionally present in thereaction, which is generally performed using similar bases, solvents andtemperatures as employed for the alkylations. For sulfonylations, whereR⁴ is SO₂R⁸, (III) is preferably a sulfonyl halide where L is preferablychlorine or bromine (more preferably chlorine). A base is optionallypresent in the reaction, which is generally performed using similarbases, solvents and temperatures as employed for the alkylations.

For reactions in which R⁴ is P(═X)(—YR⁸)(-ZR^(8a)), wherein R⁸, R^(8a),X, Y and Z are as defined above, L is preferably halogen (morepreferably chlorine). The reaction is generally performed in thepresence of a base, in an inert solvent such as tetrahydrofuran, dioxan,acetonitrile, toluene, dichloroethane, dimethylsulfoxide orN,N-dimethylformamide, at a temperature of from 0° C. to 150° C.,preferably from 20° C. to 100° C. The base is generally an alkali metalhydride such as sodium hydride, or an organic base such as1,8-diazabicyclo[5.4.0]undec-7-en (DBU), or a tertiary amine for exampletriethylamine or ethyldiisopropylamine, optionally in the presence of acatalyst such as dimethylaminopyridine.

According to a further feature of the invention compounds of formula (I)wherein Q is CN, R¹ is CN or CF₃, and R², R³, R⁴, R⁵, W and n are asdefined above, may also be prepared by the reaction of a compound offormula (IV):

wherein L¹ is a leaving group, generally halogen and preferably Br, andthe other values are as defined above, with a compound of formula (V):R³R⁴N—H   (V)

wherein R³ and R⁴ are as defined above. The reaction is generallyperformed in the presence of a base, preferably an alkali metalphosphate such as potassium phosphate, in an inert solvent such asacetonitrile, at a temperature of from 20° C. to 100° C.

According to a further feature of the invention compounds of formula (I)wherein R⁴ is (C₂-C₄)-alkyl or (C₂-C₄)-haloalkyl which groups aresubstituted by a radical selected from the group consisting of ═N—R⁸,═NNHR⁸, ═NOR⁸, ═NOH, ═NNHC(═X)R⁸, ═NNHC(═X)NH₂, ═NNR⁸C(═X)NH₂ and═NNHC(═O)O(CH₂)_(q)R⁹, Q is CN, R¹ is CN or CF₃, and R², R³, R⁵, W and nare as defined above, may also be prepared by the reaction of acorresponding compound of formula (I) in which the (C₂-C₄)-alkyl carbonatom bearing the relevant radical is replaced by a carbon atomsubstituted by a carbonyl group or by an acetal derivative thereof(preferably a (C₁-C₄)-alkyl acetal derivative), with a compound offormula (VI), (VII), (VIII), (IX), (X), (XI), (XII) or (XIII):NH₂—R⁸   (VI)NH₂NHR⁸   (VII)NH₂OR⁸   (VIII)NH₂OH   (IX)NH₂NHC(═X)R⁸   (X)NH₂NHC(═X)NH₂   (XI)NH₂NR⁸C(═X)NH₂   (XII)NH₂NHC(═O)O(CH₂)_(q)R⁹   (XIII)

wherein the various values are as defined above, or an acid saltthereof, such as the hydrochloride salt. When the compound of formula(I) used in the reaction contains a carbon atom substituted by acarbonyl group, the reaction is generally performed in the presence of abase, in a solvent such as an alcohol for example methanol, or dioxan,at a temperature of from 0° C. to the reflux-temperature of the solvent.The base is generally an alkali metal carbonate such as potassiumcarbonate or sodium carbonate, or an organic base such as a tertiaryamine, for example triethylamine or ethyldiisopropylamine, or pyridine,or 1,8-diazabicyclo[5.4.0]undec-7-en (DBU).

When the compound of formula (I) used in the reaction contains a carbonatom substituted by an acetal moiety, the reaction is generallyperformed in the presence of a strong acid such as a mineral acid, forexample hydrochloric acid, in a solvent such as an alcohol, for examplemethanol or dioxan, at a temperature of from 0° C. to the refluxtemperature of the solvent.

According to a further feature of the invention compounds of formula (I)wherein Q and/or R¹ is CSNH₂, and the other values are as defined above,may be prepared by the reaction of the corresponding compound of formula(I) wherein Q and/or R¹ is CN, with an alkali or alkaline earth metalhydrosulfide, such as lithium, potassium, calcium or preferably sodiumhydrosulfide, in an inert solvent for example N,N-dimethylformamide,pyridine, dioxan, tetrahydrofuran, sulfolane, dimethyl sulfoxide,methanol or ethanol at a temperature from −35° C. to 50° C. preferably0° C. to 30° C. Optionally the hydrosulfide may be generated in situ bytreatment with H₂S in the presence of an organic base, such as a metalalkoxide or trialkylamine or an inorganic base, such as an alkaline oralkaline earth metal hydroxide or a carbonate, such as sodium, potassiumor ammonium carbonate. The use of a metal complexing agent, such as acrown ether, can be of benefit in accelerating the reaction. Thereaction of hydrosulfide salt with the compound of formula (I) can alsobe conducted in a two-phase water/organic solvent system using a phasetransfer catalyst such as a crown ether or a tetraalkylammonium saltsuch as tetra-n-butylammonium bromide or benzyltrimethylammoniumchloride. Organic solvents suitable for use in a two-phase system withwater include benzene, toluene, dichloromethane, 1-chlorobutane andmethyl tertiary-butyl ether.

Alternatively compounds of formula (I) wherein Q and/or R¹ is CSNH₂, mayalso be prepared from the corresponding compound of formula (I) whereinQ and/or R¹ is CN, by treatment with the reagent Ph₂PS₂, as described inTet. Lett., 24 (20), 2059 (1983).

According to a further feature of the invention compounds of formula (I)wherein Q and/or R¹ is CSNH₂, and the other values are as defined above,may be prepared by the reaction of the corresponding compound of formula(I) wherein Q and/or R¹ is CN, with a bis(trialkylsilyl)sulfide,preferably bis(trimethylsilyl)sulfide, in the presence of a basegenerally an alkali metal alkoxide such as sodium methoxide, in asolvent such as N,N-dimethylformamide, at a temperature of from 0° C. to60° C. The procedure is generally described by Lin, Ku and Shiao inSynthesis 1219 (1992).

According to a further feature of the invention compounds of formula (I)wherein n is 1 or 2, and R¹, R², R³, R⁴, R⁵ and W are as defined above,may be prepared by oxidising a corresponding compound in which n is 0or 1. The oxidation is generally performed using a peracid such as3-chloroperbenzoic acid in a solvent such as dichloromethane or1,2-dichloroethane, at a temperature of from 0° C. to the refluxtemperature of the solvent.

Intermediates of formula (II) may be prepared by the alkylation orphenylation of the corresponding compound of formula (XIV):

wherein the various values are as defined above, with a compound offormula (XV):R³-L²   (XV)

wherein R³ is as defined above and L² is a leaving group, generallyhalogen, preferably chlorine or bromine, or when R³ is a phenyl moietyis preferably fluorine. The reaction conditions used are similar tothose used for the preparation of compounds of formula (II) fromcompounds of formula (III).

Intermediates of formula (IV) may be prepared by the diazotisationreaction of the corresponding compound of formula (XIV) followed byreaction with an appropriate source of halogen, according to knownmethods.

Intermediates of formula (XIV) wherein R¹ is CN, may be prepared by thereaction of a compound of formula (XVI):

with hydroxylamine or an acid salt thereof, such as the hydrochloridesalt, in the presence of a base such as sodium bicarbonate, to give thecorresponding oxime derivative, which is then dehydrated, for example byreaction with carbonyl diimidazole in a solvent such as dichloromethane.

Intermediates of formula (XIV) wherein R¹ is CF₃, may be preparedaccording to general procedures described in EP 0372982, for example bythe reaction of a compound of formula (XVII):

with an appropriate fluorinating agent such as sulfur tetrafluorideaccording to known procedures, generally with protection of the aminogroup.

Intermediates of formula (XVII) may be prepared by oxidation ofcompounds of formula (XVI) by general procedures which are well known inthe art.

Collections of compounds of the formula (I) which can be synthesized bythe above mentioned process may also be prepared in a parallel manner,and this may be effected manually or in a semiautomated or fullyautomated manner. In this case, it is possible, for example, to automatethe procedure of the reaction, work-up or purification of the productsor of the intermediates. In total, this is to be understood as meaning aprocedure as is described, for example, by S. H. DeWitt in “AnnualReports in Combinatorial Chemistry and Molecular Diversity: AutomatedSynthesis”, Volume 1, Verlag Escom 1997, pages 69 to 77.

A series of commercially available apparatuses as are offered by, forexample, Stem Corporation, Woodrolfe Road, Tollesbury, Essex, CM9 8SE,England or H+P Labortechnik GmbH, Bruckmannring 28, 85764Oberschleiβheim, Germany or Radleys, Shirehill, Saffron Walden, Essex,England, may be used for the parallel procedure of the reaction andwork-up. For the parallel purification of compounds of the formula (I),or of intermediates obtained during the preparation, use may be made,inter alia, of chromatography apparatuses, for example those by ISCO,Inc., 4700 Superior Street, Lincoln, Nebr. 68504, USA.

The apparatuses mentioned lead to a modular procedure in which theindividual process steps are automated, but manual operations must beperformed between the process steps. This can be prevented by employingsemi-integrated or fully integrated automation systems where theautomation modules in question are operated by, for example, robots.Such automation systems can be obtained, for example, from ZymarkCorporation, Zymark Center, Hopkinton, Mass. 01748, USA.

In addition to what has been described here, compounds of the formula(I) may be prepared in part or fully by solid-phase-supported methods.For this purpose, individual intermediate steps or all intermediatesteps of the synthesis or of a synthesis adapted to suit the procedurein question are bound to a synthetic resin. Solid-phase-supportedsynthesis methods are described extensively in the specialistliterature, for example Barry A. Bunin in “The Combinatorial Index”,Academic Press, 1998.

The use of solid-phase-supported synthesis methods permits a series ofprotocols which are known from the literature and which, in turn, can beperformed manually or in an automated manner. For example, the “tea-bagmethod” (Houghten, U.S. Pat. No. 4,631,211; Houghten et al., Proc. Natl.Acad. Sci, 1985, 82, 5131-5135), in which products by IRORI, 11149 NorthTorrey Pines Road, La Jolla, Calif. 92037, USA, are employed, may besemiautomated. The automation of solid-phase-supported parallelsyntheses is performed successfully, for example, by apparatuses byArgonaut Technologies, Inc., 887 Industrial Road, San Carlos, Calif.94070, USA or MultiSynTech GmbH, Wullener Feld 4, 58454 Witten, Germany.

The preparation of the processes described herein yields compounds ofthe formula (I) in the form of substance collections which are termedlibraries. The present invention also relates to libraries whichcomprise at least two compounds of the formula (I).

Compounds of general formula (XIV) may be prepared, for exampleaccording to the general methods described in EP 0372982. Certaincompounds of formula (XIV) are novel and as such form a further part ofthe invention. A preferred novel class of such compounds are of formula(XVIII):

wherein n is 0, 1 or 2, and these compounds form a further feature ofthe invention. The compounds of formula (XVIII) also possess veryexcellent pesticidal activity, for example very good systemic control ofCtenocephalides felis (Cat flea) and contact activity againstRhipicephalus sanguineus (Brown dog tick), combined with a rapid speedof effect. Compounds of formula (XVIII) are in addition, very effectivein controlling pest species which are important for crop protection.

Compounds of formula (Ill), (V), (VI), (VII), (VIII), (IX), (X), (XI),(XII), (XIII), (XV), (XVI) and (XVII) are known or may be prepared byknown methods.

The following non-limiting Examples illustrate the preparation of thecompounds of formula (I).

CHEMICAL EXAMPLES

NMR spectra were run in deuterochloroform unless stated otherwise. Inthe Examples which follow, quantities (also percentages) are weightbased, unless stated otherwise. Ratios of solvents are volume based.

Example 11-(2,6-Dichloro-4-trifluoromethylphenyl)-2,3-dicyano-4-trifluoromethylsulfinyl-5-N-methyl-N-(2-methylthioethyl)aminopyrrole

A mixture of1-(2,6-dichloro-4-trifluoromethylphenyl)-2,3-dicyano-4-trifluoromethylsulfinyl-5-N-methylaminopyrrole(95 mg, 0.2 mmol), 2-chloroethyl methylsulfide (27 mg, 0.2 mmol), andpotassium phosphate (131 mg, 0.6 mmol) in acetonitrile (10 mL) washeated under reflux for 2.25 hour. It was then cooled and poured intoethyl acetate and saturated ammonium chloride. The organic layer waswashed with water, brine, dried (sodium sulfate), concentrated andpurified by chromatography on a silica gel column, eluting withheptane/ethyl acetate (4:1 to 2:1), to give the title compound as anorange oil (Compound 1.4, 62.1 mg, 0.113 mmol); 19F-NMR: −64.20, −72.16.

Example 21-(2,6-Dichloro-4-trifluoromethylphenyl)-2,3-dicyano-4-trifluoromethylsulfinyl-5-N-methyl-N-(2-methylsulfinylethyl)aminopyrroleand1-(2,6-dichloro-4-trifluoromethylphenyl)-2,3-dicyano-4-trifluoromethylsulfinyl-5-N-methyl-N-(2-methylsulfonylethyl)aminopyrrole

m-Chloroperbenzoic acid (38 mg, 70%, 0.15 mmol) was added to a solutionof1-(2,6-dichloro-4-trifluoromethylphenyl)-2,3-dicyano-4-trifluoromethylsulfinyl-5-N-methyl-N-(2-methylthioethyl)aminopyrrole(56 mg, 0.1 mmol) in 1,2-dichloroethane (10 ml) at 20° C., and theresulting mixture stirred at 20° C. for one hour, then poured into 2Nsodium hydroxide solution and ethyl acetate. The organic layer washedwith water, brine, dried (sodium sulfate), and concentrated and purifiedby chromatography on a silica gel column eluting with heptane/ethylacetate (1:2 to 1:9.5), to give1-(2,6-dichloro-4-trifluoromethylphenyl)-2,3-dicyano-4-trifluoromethylsulfinyl-5-N-methyl-N-(2-methylsulfonylethyl)aminopyrroleas a moist white solid (Compound 1.6, 15.2 mg, 26%), 19F-NMR: −63.79,−71.68. Further elution gave1-(2,6-dichloro-4-trifluoromethylphenyl)-2,3-dicyano-4-trifluoromethylsulfinyl-5-N-methyl-N-(2-methylsulfinylethyl)aminopyrroleas a light yellow moist solid (Compound 1.5, 41.2 mg, 74%); 19F-NMR:−63.75, −63.76, −71.74, −71.81.

The following Intermediate Examples illustrate the preparation ofintermediates used in the synthesis of the above Examples.

Intermediate Example 15-Amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-2,3-dicyano-4-trifluoromethylsulfinylpyrrole

Hydrogen peroxide (278 mg, 35%, 2.9 mmol) was added to solution of5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-2,3-dicyano-4-trifluoromethylthiopyrrole(850 mg, 1.9 mmol) in trifluoroacetic acid (10 ml). The resultingsolution was stirred at 20° C. for 0.75 hour. Another portion ofhydrogen peroxide ( 0.97 mmol) was added and the mixture stirred at 20°C. for a further hour. The reaction mixture was poured into methylenechloride (60 ml) and water (60 ml) and the organic layer washed withwater (2×), dried (sodium sulfate), concentrated and purified bychromatography on silica gel, eluting with heptane/ethyl acetate (4:1)to give the title compound as a yellow solid (293 mg, 0.64 mmol);19F-NMR: −64.35, −75.59.

Intermediate Example 21-(2,6-Dichloro-4-trifluoromethylphenyl)-2,3-dicyano-4-trifluoromethylsulfinyl-5-N-methylaminopyrrole

Sodium borohydride (0.075 g, 1.9 mmol) was added to a solution of1-(2,6-dichloro-4-trifluoromethylphenyl)-2,3-dicyano-4-trifluoromethylsulfinyl-5-ethoxymethyleneaminopyrrole(0.325 g, 0.6 mmol) in ethanol (60 ml) at 6° C., and the resultingmixture stirred at 6-12° C. for 1.25 hours then for 0.5 hour at 12° C. Afurther quantity of sodium borohydride (0.05 g, 1.27 mmol) in ethanolwas added and after a total of four hours at 20° C. the mixture waspoured into ethyl acetate and water. The organic layer was dried (sodiumsulfate), concentrated and purified by chromatography on a silica gelcolumn, eluting with heptane/ethyl acetate (4:1 to 2:1) to give thetitle compound as a yellow solid (154.2 mg, 0.32 mmol); mp. 90-110° C.;

19F-NMR: −64.23, −75.16.

Intermediate Example 31-(2,6-Dichloro-4-trifluoromethylphenyl)-2,3-dicyano-4-trifluoromethylsulfinyl-5-ethoxymethyleneaminopyrrole

A mixture of5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-2,3-dicyano-4-trifluoromethylsulfinylpyrrole(290 mg, 0.6 mmol), triethyl orthoformate (4.45 g, 29.7 mmol), andp-toluenesulfonic acid (10 mg, 0.1 mmol) was heated at 100° C. for 40minutes, then at 120° C. for 70 minutes. Additional p-toluenesulfonicacid (a catalytic amount) was added and the resulting mixture was heatedat 120° C. for 2.4 hour. It was then concentrated to dryness and dilutedwith dichloromethane (20 ml). The organic layer was washed withsaturated sodium bicarbonate, brine, dried (sodium sulfate), andconcentrated to afford the title compound as an orange oil which wasused without purification for the next transformation. 19F-NMR: −64.23,−72.08.

Intermediate Example 45-Amino-1-(2,6-dichloro-4-trifluoromethylphenyl]-3-cyano-2-[(E/Z)-(hydroxyimino)methyl]-4-trifluoromethylthio-1H-pyrrole

Hydroxylamine hydrochloride (0.44 g, 6.9 mmol) in water (3 ml) was addedto a solution of5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-2-formyl-4-trifluoromethylthio-1H-pyrrole(2.1 g, 4.2 mmol) in ethanol (35 ml) and stirred for five minutes. Asolution of sodium bicarbonate (0.53 g, 6.3 mmol) in water (3 ml) wasadded and the mixture stirred at 20° C. overnight. A further portion ofhydroxylamine hydrochloride (0.44 g) in water (3 ml) was added and theresulting mixture stirred at 20° C. overnight. It was then concentratedand diluted with ethyl acetate. The organic layer was washed with water(2×) and the combined aqueous layer extracted twice with ethyl acetate.The combined organic layer was dried, concentrated, and used directlyfor the subsequent reaction.

Intermediate Example 55-Amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-2,3-dicyano-4-trifluoromethylthio-1H-pyrrole

Carbonyl diimidazole (0.5 g, 3.1 mmol) was added to a solution of5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl]-3-cyano-2-[(E/Z)-(hydroxyimino)methyl]-4-trifluoromethylthio-1H-pyrrole(1.2 g, 2.6 mmol) in methylene chloride (10 ml) and stirred at 20° C.for three days. It was then added to 10% aqueous hydrochloric acidsolution (18 ml) and stirred for 5 minutes. The organic layer was washedwith water (2×), brine, dried (magnesium sulfate), concentrated andpurified by chromatography using a silica gel column eluting withcyclohexane/ethyl acetate (8/2) to give the title compound as a yellowsolid (700 mg, 61% yield), mp. 175-177° C.

Intermediate Example 65-Amino-1-(2,6-dichloro-4-trifluoromethylphenyl-2,3-dicyano)-4-trifluoromethylsulfonyl-1H-pyrrole

Peracetic acid (35% in dilute acetic acid, 327 mg, 1.55 mmol) was addeddropwise to a solution of5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-2,3-dicyano-4-trifluoromethylthiopyrrole(58 mg, 0.13 mmol) in 1,2-dichloroethane (10 ml) during a period of 21.5hours of heating under reflux. The reaction mixture was then cooled andconcentrated, then toluene (2.5 ml) added and concentrated again. Theresidue was purified by chromatography via silica gel column elutingwith heptane/ethyl acetate (4/1) to give the title compound as an offwhite solid (16.5 mg, 0.034 mmol), mp. 190-199° C.

The following preferred compounds shown in Tables I to 4 also form partof the present invention, and were or may be prepared in accordancewith, or analogously to, the above-mentioned Examples 1 to 2 or theabove-described general methods. In the Tables Me means methyl, Et meansethyl, Pr means n-propyl, cPr means cyclopropyl, OMe means methoxy, OEtmeans ethoxy, Ph means phenyl and CH2CH2CH═NNHCO(4-Cl Ph) means a3-(4-chlorobenzoylhydrazono)propyl group. 19F-NMR spectra shift valuesare given in ppm.

Compound numbers are given for reference purposes only. TABLE ICompounds of formula (I) in which the substituents have the followingmeanings: Q is CN, R¹ is CN, R² is CF₃, W is C—Cl, R³ is CH₃, R⁵ is CF₃Cpd No n R⁴ mp/19F-NMR 1.1 0 CH2CH2SCH3 1.2 0 CH2CH2SOCH3 1.3 0CH2CH2SO2CH3 1.4 1 CH2CH2SCH3 −64.20, −72.16 1.5 1 CH2CH2SOCH3 −63.75,−63.76, −71.74, −71.81 1.6 1 CH2CH2SO2CH3 −63.79, −71.68 1.7 2CH2CH2SCH3 1.8 2 CH2CH2SOCH3 1.9 2 CH2CH2SO2CH3 1.10 0 COCH2OEt 1.11 1COCH2OEt 1.12 2 COCH2OEt 1.13 0 CH2CH═NOEt 1.14 1 CH2CH═NOCH2cPr 1.15 2COOCH2Ph 1.16 0 CH2CH═NNHCO(4-EtOPh) 1.17 1 CH2CH═NNHCO-nBu 1.18 2CH2CH(OCH3)2 1.19 0 CH2CH(SCH3)2 1.20 1 CH2CH(SCH3)(SOCH3) 1.21 2CH2CH2CH(OCH3)2 1.22 0 CH2CH2CH2SCH3 1.23 0 CH2CH2CH2SOCH3 1.24 0CH2CH2CH2SO2CH3 1.25 1 CH2CH2CH═NOCH2CH3 1.26 1 CH2CH2CH═NNHCO(4-ClPh)1.27 1 CH2CH2CH═NNHCSNH2 1.28 2 CH2CH═NNHCSNH2 1.29 2CH2(1,3-dioxolan-2-yl) 1.30 2 CH2(1,3-dithiolan-2-yl) 1.31 1CH2CH2(1,3-dithiolan-2-yl) 1.32 2 CH2(1,3-dithian-2-yl) 1.33 1CH2CH2(1,3-dithian-2-yl)

TABLE 2 Compounds of formula (I) in which the substituents have thefollowing meanings: Q is CN, R¹ is CN, R² is CF₃, W is C—N(CH3)(CH2CH3),R³ is CH₃, R⁵ is CF₃ Cpd No n R⁴ mp/19F-NMR 2.1 0 CH2CH2SCH3 2.2 0CH2CH2SOCH3 2.3 0 CH2CH2SO2CH3 2.4 1 CH2CH2SCH3 2.5 1 CH2CH2SOCH3 2.6 1CH2CH2SO2CH3 2.7 2 CH2CH2SCH3 2.8 2 CH2CH2SOCH3 2.9 2 CH2CH2SO2CH3 2.100 COCH2OEt 2.11 1 COCH2OEt 2.12 2 COCH2OEt 2.13 0 CH2CH═NOEt 2.14 1CH2CH═NOCH2cPr 2.15 2 COOCH2Ph 2.16 0 CH2CH═NNHCO(4-EtOPh) 2.17 1CH2CH═NNHCO-nBu 2.18 2 CH2CH(OCH3)2 2.19 0 CH2CH(SCH3)2 2.20 1CH2CH(SCH3)(SOCH3) 2.21 2 CH2CH2CH(OCH3)2 2.22 0 CH2CH2CH2SCH3 2.23 0CH2CH2CH2SOCH3 2.24 0 CH2CH2CH2SO2CH3 2.25 1 CH2CH2CH═NOCH2CH3 2.26 1CH2CH2CH═NNHCO(4-ClPh) 2.27 1 CH2CH2CH═NNHCSNH2 2.28 2 CH2CH═NNHCSNH22.29 2 CH2(1,3-dioxolan-2-yl) 2.30 2 CH2(1,3-dithiolan-2-yl) 2.31 1CH2CH2(1,3-dithiolan-2-yl) 2.32 2 CH2(1,3-dithian-2-yl) 2.33 1CH2CH2(1,3-dithian-2-yl)

TABLE 3 Compounds of formula (I) in which the substituents have thefollowing meanings: Q is CN, R¹ is CN, R² is CF₃, W is C—Cl, R³ isCH₂-cyclopropyl, R⁵ is CF₃ Cpd No n R⁴ mp/19F-NMR 3.1 0 CH2CH2SCH3 3.2 0CH2CH2SOCH3 3.3 0 CH2CH2SO2CH3 3.4 1 CH2CH2SCH3 3.5 1 CH2CH2SOCH3 3.6 1CH2CH2SO2CH3 3.7 2 CH2CH2SCH3 3.8 2 CH2CH2SOCH3 3.9 2 CH2CH2SO2CH3 3.100 COCH2OEt 3.11 1 COCH2OEt 3.12 2 COCH2OEt 3.13 0 CH2CH═NOEt 3.14 1CH2CH═NOCH2cPr 3.15 2 COOCH2Ph 3.16 0 CH2CH═NNHCO(4-EtOPh) 3.17 1CH2CH═NNHCO-nBu 3.18 2 CH2CH(OCH3)2 3.19 0 CH2CH(SCH3)2 3.20 1CH2CH(SCH3)(SOCH3) 3.21 2 CH2CH2CH(OCH3)2 3.22 0 CH2CH2CH2SCH3 3.23 0CH2CH2CH2SOCH3 3.24 0 CH2CH2CH2SO2CH3 3.25 1 CH2CH2CH═NOCH2CH3 3.26 1CH2CH2CH═NNHCO(4-ClPh) 3.27 1 CH2CH2CH═NNHCSNH2 3.28 2 CH2CH═NNHCSNH23.29 2 CH2(1,3-dioxolan-2-yl) 3.30 2 CH2(1,3-dithiolan-2-yl) 3.31 1CH2CH2(1,3-dithiolan-2-yl) 3.32 2 CH2(1,3-dithian-2-yl) 3.33 1CH2CH2(1,3-dithian-2-yl)

TABLE 4 Compounds of formula (I) in which the substituents have thefollowing meanings: Q is CN, R¹ is CN, R² is CF₃, W is N, R³ is CH₃, R⁵is CF₃ Cpd No n R⁴ mp/19F-NMR 4.1 0 CH2CH2SCH3 4.2 0 CH2CH2SOCH3 4.3 0CH2CH2SO2CH3 4.4 1 CH2CH2SCH3 4.5 1 CH2CH2SOCH3 4.6 1 CH2CH2SO2CH3 4.7 2CH2CH2SCH3 4.8 2 CH2CH2SOCH3 4.9 2 CH2CH2SO2CH3 4.10 0 COCH2OEt 4.11 1COCH2OEt 4.12 2 COCH2OEt 4.13 0 CH2CH═NOEt 4.14 1 CH2CH═NOCH2cPr 4.15 2COOCH2Ph 4.16 0 CH2CH═NNHCO(4-EtOPh) 4.17 1 CH2CH═NNHCO-nBu 4.18 2CH2CH(OCH3)2 4.19 0 CH2CH(SCH3)2 4.20 1 CH2CH(SCH3)(SOCH3) 4.21 2CH2CH2CH(OCH3)2 4.22 0 CH2CH2CH2SCH3 4.23 0 CH2CH2CH2SOCH3 4.24 0CH2CH2CH2SO2CH3 4.25 1 CH2CH2CH═NOCH2CH3 4.26 1 CH2CH2CH═NNHCO(4-ClPh)4.27 1 CH2CH2CH═NNHCSNH2 4.28 2 CH2CH═NNHCSNH2 4.29 2CH2(1,3-dioxolan-2-yl) 4.30 2 CH2(1,3-dithiolan-2-yl) 4.31 1CH2CH2(1,3-dithiolan-2-yl) 4.32 2 CH2(1,3-dithian-2-yl) 4.33 1CH2CH2(1,3-dithian-2-yl)

According to a further feature of the present invention there isprovided a method for the control of pests at a locus which comprisesapplying thereto an effective amount of a compound of formula (I) or asalt thereof. For this purpose, the said compound is normally used inthe form of a pesticidal composition (i.e. in association withcompatible diluents or carriers and/or surface active agents suitablefor use in pesticidal compositions), for example as hereinafterdescribed.

The term “compound of the invention” as used hereinafter embraces a1-aryl-5-disubstituted-aminopyrrole of formula (I) as defined above anda pesticidally acceptable salt thereof.

One aspect of the present invention as defined above is a method for thecontrol of pests at a locus. The locus includes, for example, the pestitself, the place (plant, field, forest, orchard, waterway, soil, plantproduct, or the like) where the pest resides or feeds, or a placesusceptible to future infestation by the pest. The compound of theinvention may therefore be applied directly to the pest, to the placewhere the pest resides or feeds, or to the place susceptible to futureinfestation by the pest.

As is evident from the foregoing pesticidal uses, the present inventionprovides pesticidally active compounds and methods of use of saidcompounds for the control of a number of pest species which includes:arthropods, especially insects or mites, or plant nematodes. Thecompound of the invention may thus be advantageously employed inpractical uses, for example, in agricultural or horticultural crops, inforestry, in veterinary medicine or livestock husbandry, or in publichealth.

The compounds of the invention may be used for example in the followingapplications and on the following pests:

For the control of soil insects, such as corn rootworm, termites(especially for protection of structures), root maggots, wireworms, rootweevils, stalkborers, cutworms, root aphids, or grubs. They may also beused to provide activity against plant pathogenic nematodes, such asroot-knot, cyst, dagger, lesion, or stem or bulb nematodes, or againstmites. For the control of soil pests, for example corn rootworm, thecompounds are advantageously applied to or incorporated at an effectiverate into the soil in which crops are planted or to be planted or to theseeds or growing plant roots.

In the area of public health, the compounds are especially useful in thecontrol of many insects, especially filth flies or other Dipteran pests,such as houseflies, stableflies, soldierflies, hornflies, deerflies,horseflies, midges, punkies, blackflies, or mosquitoes.

In the protection of stored products, for example cereals, includinggrain or flour, groundnuts, animal feedstuffs, timber or householdgoods, e.g. carpets and textiles, compounds of the invention are usefulagainst attack by arthropods, more especially beetles, includingweevils, moths or mites, for example Ephestia spp. (flour moths),Anthrenus spp. (carpet beetles), Tribolium spp. (flour beetles),Sitophilus spp. (grain weevils) or Acarus spp. (mites).

In the control of cockroaches, ants or termites or similar arthropodpests in infested domestic or industrial premises or in the control ofmosquito larvae in waterways, wells, reservoirs or other running orstanding water.

For the treatment of foundations, structures or soil in the preventionof the attack on building by termites, for example, Reticulitermes spp.,Heterotermes spp., Coptotermes spp.

In agriculture against adults, larvae and eggs of Lepidoptera(butterflies and moths), e.g. Heliothis spp. such as Heliothis virescens(tobacco budworm), Heliothis armigera and Heliothis zea. Against adultsand larvae of Coleoptera (beetles) e.g. Anthonomus spp. e.g. grandis(cotton boll weevil), Leptinotarsa decemlineata (Colorado potatobeetle), Diabrotica spp. (corn rootworms). Against Heteroptera(Hemiptera and Homoptera) e.g. Psylla spp., Bemisia spp., Trialeurodesspp., Aphis spp., Myzus spp., Megoura viciae, Phylloxera spp.,Nephotettix spp. (rice leaf hoppers), Nilaparvata spp.

Against Diptera e.g. Musca spp. Against Thysanoptera such as Thripstabaci.

Against Orthoptera such as Locusta and Schistocerca spp., (locusts andcrickets) e.g. Gryllus spp., and Acheta spp. for example, Blattaorientalis, Periplaneta americana, Blatella germanica, Locustamigratoria migratorioides, and Schistocerca gregaria. Against Collembolae.g. Periplaneta spp. and Blatella spp. (roaches).

Against arthropods of agricultural significance such as Acari (mites)e.g. Tetranychus spp., and Panonychus spp.

Against nematodes which attack plants or trees of importance toagriculture, forestry or horticulture either directly or by spreadingbacterial, viral, mycoplasma or fungal diseases of the plants. Forexample root-knot nematodes such as Meloidogyne spp. (e.g. M.incognita).

In the field of veterinary medicine or livestock husbandry or in themaintenance of public health against arthropods which are parasiticinternally or externally upon vertebrates, particularly warm-bloodedvertebrates, for example domestic animals, e.g. cattle, sheep, goats,equines, swine, poultry, dogs or cats, for example Acarina, includingticks (e.g. soft-bodied ticks including Argasidae spp. e.g. Argas spp.and Ornithodorus spp. (e.g. Ornithodorus moubata); hard-bodied ticksincluding Ixodidae spp., e.g. Boophilus spp. e.g. Boophilus microplus,Rhipicephalus spp. e.g. Rhipicephalus appendiculatus and Rhipicephalussanguineus; mites (e.g. Damalinia spp.); fleas (e.g. Ctenocephalidesspp. e.g. Ctenocephalides felis (cat flea) and Ctenocephalides canis(dog flea)); lice e.g. Menopon spp.; Diptera (e.g. Aedes spp., Anophelesspp., Musca spp., Hypoderma spp.); Hemiptera; Dictyoptera (e.g.Periplaneta spp., Blatella spp.); Hymenoptera; for example againstinfections of the gastro-intestinal tract caused by parasitic nematodeworms, for example members of the family Trichostrongylidae.

In a preferred aspect of the invention the compounds of formula (I) areused for the control of parasites of animals. Preferably the animal tobe treated is a domestic companion animal such as a dog or a cat.

In a further aspect of the invention the compounds of formula (I) orsalts or compositions thereof are used for the preparation of aveterinary medicament.

A further feature of the invention thus relates to the use of a compoundof formula (I) or a salt thereof, or of a composition thereof, for thecontrol of pests.

In practical use for the control of arthropods, especially insects ormites, or helminths, especially nematode pests of plants, a method, forexample, comprises applying to the plants or to the medium in which theygrow an effective amount of a compound of the invention. For such amethod, the compound of the invention is generally applied to the locusin which the arthropod or nematode infestation is to be controlled at aneffective rate in the range of about 2 g to about 1 kg of the activecompound per hectare of locus treated. Under ideal conditions, dependingon the pest to be controlled, a lower rate may offer adequateprotection. On the other hand, adverse weather conditions, resistance ofthe pest or other factors may require that the active ingredient be usedat higher rates. The optimum rate depends usually upon a number offactors, for example, the type of pest being controlled, the type or thegrowth stage of the infested plant, the row spacing or also the methodof application. Preferably an effective rate range of the activecompound is from about 10 g/ha to about 400 g/ha, more preferably fromabout 50 g/ha to about 200 g/ha.

When a pest is soil-borne, the active compound generally in a formulatedcomposition, is distributed evenly over the area to be treated (ie, forexample broadcast or band treatment) in any convenient manner and isapplied at rates from about 10 g/ha to about 400 g ai/ha, preferablyfrom about 50 g/ha to about 200 g ai/ha. When applied as a root dip toseedlings or drip irrigation to plants the liquid solution or suspensioncontains from about 0.075 to about 1000 mg ai/l, preferably from about25 to about 200 mg ai/l. Application may be made, if desired, to thefield or crop-growing area generally or in close proximity to the seedor plant to be protected from attack. The compound of the invention canbe washed into the soil by spraying with water over the area or can beleft to the natural action of rainfall. During or after application, theformulated compound can, if desired, be distributed mechanically in thesoil, for example by ploughing, disking, or use of drag chains.Application can be prior to planting, at planting, after planting butbefore sprouting has taken place, or after sprouting.

The compound of the invention and methods of control of pests therewithare of particular value in the protection of field, forage, plantation,glasshouse, orchard or vineyard crops, of ornamentals, or of plantationor forest trees, for example: cereals (such as wheat or rice), cotton,vegetables (such as peppers), field crops (such as sugar beets, soybeansor oil seed rape), grassland or forage crops (such as maize or sorghum),orchards or groves (such as of stone or pit fruit or citrus), ornamentalplants, flowers or vegetables or shrubs under glass or in gardens orparks, or forest trees (both deciduous and evergreen) in forests,plantations or nurseries.

They are also valuable in the protection of timber (standing, felled,converted, stored or structural) from attack, for example, by sawfliesor beetles or termites. They have applications in the protection ofstored products such as grains, fruits, nuts, spices or tobacco, whetherwhole, milled or compounded into products, from moth, beetle, mite orgrain weevil attack. Also protected are stored animal products such asskins, hair, wool or feathers in natural or converted form (e.g. ascarpets or textiles) from moth or beetle attack as well as stored meat,fish or grains from beetle, mite or fly attack.

Additionally, the compound of the invention and methods of use thereofare of particular value in the control of arthropods or helminths whichare injurious to, or spread or act as vectors of diseases domesticanimals, for example those hereinbefore mentioned, and more especiallyin the control of ticks, mites, lice, fleas, midges, or biting, nuisanceor myiasis flies. The compounds of the invention are particularly usefulin controlling arthropods or helminths which are present inside domestichost animals or which feed in or on the skin or suck the blood of theanimal, for which purpose they may be administered orally, parenterally,percutaneously or topically.

The compositions hereinafter described for application to growing cropsor crop growing loci or as a seed dressing may, in general,alternatively be employed in the protection of stored products,household goods, property or areas of the general environment. Suitablemeans of applying the compounds of the invention include: to growingcrops as foliar sprays (for example as an in-furrow spray), dusts,granules, fogs or foams or also as suspensions of finely divided orencapsulated compositions as soil or root treatments by liquid drenches,dusts, granules, smokes or foams; to seeds of crops via application asseed dressings, e.g. by liquid slurries or dusts;

to animals infested by or exposed to infestation by arthropods orhelminths, by parenteral, oral or topical application of compositions inwhich the active ingredient exhibits an immediate and/or prolongedaction over a period of time against the arthropods or helminths, forexample by incorporation in feed or suitable orally-ingestiblepharmaceutical formulations, edible baits, salt licks, dietarysupplements, pour-on formulations, sprays, baths, dips, showers, jets,dusts, greases, shampoos, creams, wax smears or livestock self-treatmentsystems;

to the environment in general or to specific locations where pests maylurk, including stored products, timber, household goods, or domestic orindustrial premises, as sprays, fogs, dusts, smokes, wax-smears,lacquers, granules or baits, or in tricklefeeds to waterways, wells,reservoirs or other running or standing water.

The compounds of formula (I) are particularly useful for the control ofparasites of animals when applied orally, and in a further preferredaspect of the invention the compounds of formula (I) are used for thecontrol of parasites of animals by oral application. The compounds ofthe formula (I) or salts thereof may be administered before, during orafter meals. The compounds of the formula (I) or salts thereof may bemixed with a carrier and/or foodstuff.

The compound of the formula (I) or salt thereof is administered orallyin a dose to the animal in a dose range generally from 0.1 to 500 mg/kgof the compound of the formula (I) or salt thereof per kilogram ofanimal body weight (mg/kg).

The frequency of treatment of the animal, preferably the domestic animalto be treated by the compound of the formula (I) or salt thereof isgenerally from about once per week to about once per year, preferablyfrom about once every two weeks to once every three months.

The compounds of the invention may be administered most advantageouslywith another parasiticidally effective material, such as anendoparasiticide, and/or an ectoparasiticide, and/or anendectoparasiticide. For example, such compounds include macrocycliclactones such as avermectins or milbemycins e.g., ivermectin, pyratel oran insect growth regulator such as lufenuron or methoprene.

The compounds of the formula (I) can also be employed for controllingharmful organisms in crops of known genetically engineered plants orgenetically engineered plants yet to be developed. As a rule, thetransgenic plants are distinguished by especially advantageousproperties, for example by resistances to particular crop protectionagents, resistances to plant diseases or pathogens of plant diseases,such as particular insects or microorganisms such as fungi, bacteria orviruses. Other particular properties concern, for example, the harvestedmaterial with regard to quantity, quality, storage properties,composition and specific constituents. Thus, transgenic plants are knownwhere the starch content is increased, or the starch quality is altered,or where the harvested material has a different fatty acid composition.

The use in economically important transgenic crops of useful plants andornamentals is preferred, for example of cereals such as wheat, barley,rye, oats, millet, rice, cassava and maize or else crops of sugar beet,cotton, soya, oilseed rape, potatoes, tomatoes, peas and other types ofvegetables.

When used in transgenic crops, in particular those which haveresistances to insects, effects are frequently observed, in addition tothe effects against harmful organisms to be observed in other crops,which are specific for application in the transgenic crop in question,for example an altered or specifically widened spectrum of pests whichcan be controlled, or altered application rates which may be employedfor application.

The invention therefore also relates to the use of compounds of theformula (I) for controlling harmful organisms in transgenic crop plants.

According to a further feature of the present invention there isprovided a pesticidal composition comprising one or more compounds ofthe invention as defined above, in association with, and preferablyhomogeneously dispersed in one or more compatible pesticidallyacceptable diluents or carriers and/or surface active agents [i.e.diluents or carriers and/or surface active agents of the type generallyaccepted in the art as being suitable for use in pesticidal compositionsand which are compatible with compounds of the invention].

In practice, the compounds of the invention most frequently form partsof compositions. These compositions can be employed to controlarthropods, especially insects, or plant nematodes or mites. Thecompositions may be of any type known in the art suitable forapplication to the desired pest in any premises or indoor or outdoorarea. These compositions contain at least one compound of the inventionas the active ingredient in combination or association with one or moreother compatible components which are for example, solid or liquidcarriers or diluents, adjuvants, surface-active-agents, or the likeappropriate for the intended use and which are agronomically ormedicinally acceptable. These compositions, which may be prepared by anymanner known in the art, likewise form a part of this invention.

The compounds of the invention, in their commercially availableformulations and in the use forms prepared from these formulations maybe present in mixtures with other active substances such asinsecticides, attractants, sterilants, acaricides, nematicides,fungicides, growth regulatory substances or herbicides.

The pesticides include, for example, phosphoric esters, carbamates,carboxylic esters, formamidines, tin compounds and materials produced bymicroorganisms.

Preferred components in mixtures are:

Insecticides/Acaricides/Nematicides:

1. Acetylcholinesterase (AChE) inhibitors

1.1 carbamates (for example alanycarb, aldicarb, aldoxycarb, allyxycarb,aminocarb, azamethiphos, bendiocarb, benfuracarb, bufencarb, butacarb,butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan,chloethocarb, coumaphos, cyanofenphos, cyanophos, dimetilan,ethiofencarb, fenobucarb, fenothiocarb, formetanate, furathiocarb,isoprocarb, metam-sodium, methiocarb, methomyl, metolcarb, oxamyl,pirimicarb, promecarb, propoxur, thiodicarb, thiofanox, triazamate,trimethacarb, XMC, xylylcarb)

1.2 organophosphates (for example acephate, azamethiphos, azinphos(-methyl, -ethyl), bromophos-ethyl, bromfenvinfos (-methyl),butathiofos, cadusafos, carbophenothion, chlorethoxyfos,chlorfenvinphos, chlormephos, chlorpyrifos (-methyl/-ethyl), coumaphos,cyanofenphos, cyanophos, demeton-s-methyl, demeton-s-methylsulphon,dialifos, diazinon, dichlofenthion, dichlorvos/DDVP, dicrotophos,dimethoate, dimethylvinphos, dioxabenzofos, disulfoton, EPN, ethion,ethoprophos, etrimfos, famphur, fenamiphos, fenitrothion, fensulfothion,fenthion, flupyrazofos, fonofos, formothion, fosmethilan, fosthiazate,heptenophos, iodofenphos, iprobenfos, isazofos, isofenphos, isopropylo-salicylate, isoxathion, malathion, mecarbam, methacrifos,methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate,oxydemeton-methyl, parathion (-methyl/-ethyl), phenthoate, phorate,phosalone, phosmet, phosphamidon, phosphocarb, phoxim, pirimiphos(-methyl/-ethyl), profenofos, propaphos, propetamphos, prothiofos,prothoate, pyraclofos, pyridaphenthion, pyridathion, quinalphos,sebufos, sulfotep, sulprofos, tebupirimfos, temephos, terbufos,tetrachlorvinphos, thiometon, triazophos, triclorfon, vamidothion)

2. Sodium channel modulators/voltage-dependent sodium channel blockers

2.1 pyrethroids (for example acrinathrin, allethrin (d-cis-trans,d-trans), beta-cyfluthrin, bifenthrin, bioallethrin,bioallethrin-s-cyclopentyl-isomer, bioethanomethrin, biopermethrin,bioresmethrin, chlovaporthrin, cis-cypermethrin, cis-resmethrin,cis-permethrin, clocythrin, cycloprothrin, cyfluthrin, cyhalothrin,cypermethrin (alpha-, beta-, theta-, zeta-), cyphenothrin, DDT,deltamethrin, empenthrin (1R-isomer), esfenvalerate, etofenprox,fenfluthrin, fenpropathrin, fenpyrithrin, fenvalerate, flubrocythrinate,flucythrinate, flufenprox, flumethrin, fluvalinate, fubfenprox,gamma-cyhalothrin, imiprothrin, kadethrin, lambda-cyhalothrin,metofluthrin, permethrin (cis-, trans-), phenothrin (1R-trans isomer),prallethrin, profluthrin, protrifenbute, pyresmethrin, resmethrin, RU15525, silafluofen, tau-fluvalinate, tefluthrin, terallethrin,tetramethrin (1R-isomer), tralomethrin, transfluthrin, ZXI 8901,pyrethrins (pyrethrum))

2.2 oxadiazines (for example indoxacarb)

3. Acetylcholine receptor agonists/antagonists

3.1 chloronicotinyls/neonicotinoids (for example acetamiprid,clothianidin, dinotefuran, imidacloprid, nitenpyram, nithiazine,thiacloprid, thiamethoxam)

3.2 nicotine, bensultap, cartap

4. Acetylcholine receptor modulators

4.1 spinosyns (for example spinosad)

5. GABA-controlled chloride channel antagonists

5.1 cyclodiene organochlorines (for example camphechlor, chlordane,endosulfan, gamma-HCH, HCH, heptachlor, lindane, methoxychlor)

5.2 fiproles (for example acetoprole, ethiprole, fipronil, vaniliprole)

6. Chloride channel activators

6.1 mectins (for example abamectin, avermectin, emamectin,emamectin-benzoate, ivermectin, milbemectin, milbemycin)

7. Juvenile hormone mimetics

(for example diofenolan, epofenonane, fenoxycarb, hydroprene, kinoprene,methoprene, pyriproxifen, triprene)

8. Ecdysone agonists/disruptors

8.1 diacylhydrazines (for example chromafenozide, halofenozide,methoxyfenozide, tebufenozide)

9. Chitin biosynthesis inhibitors

9.1 benzoylureas (for example bistrifluron, chlofluazuron,diflubenzuron, fluazuron, flucycloxuron, flufenoxuron, hexaflumuron,lufenuron, novaluron, noviflumuron, penfluron, teflubenzuron,triflumuron)

9.2 buprofezin

9.3 cyromazine

10. Inhibitors of oxidative phosphorylation, ATP disruptors

10.1 diafenthiuron

10.2 organotins (for example azocyclotin, cyhexatin, fenbutatin-oxide)

11. Decouplers of oxidative phosphorylation acting by interrupting theH-proton gradient

11.1 pyrroles (for example chlorfenapyr)

11.2 dinitrophenols (for example binapacyrl, dinobuton, dinocap, DNOC)

12. Site-I electron transport inhibitors

12.1 METIs (for example fenazaquin, fenpyroximate, pyrimidifen,pyridaben, tebufenpyrad, tolfenpyrad)

12.2 hydramethylnone

12.3 dicofol

13. Site-II electron transport inhibitors

13.1 rotenone

14. Site-III electron transport inhibitors

14.1 acequinocyl, fluacrypyrim

15. Microbial disruptors of the insect gut membrane

Bacillus thuringiensis strains

16. Inhibitors of fat synthesis

16.1 tetronic acids (for example spirodiclofen, spiromesifen)

16.2 tetramic acids [for example3-(2,5-dimethylphenyl)-8-methoxy-2-oxo-1-azaspiro[4.5]dec-3-en-4-ylethyl carbonate (alias: carbonic acid,3-(2,5-dimethylphenyl)-8-methoxy-2-oxo-1-azaspiro[4.5]dec-3-en-4-ylethyl ester, CAS Reg. No.: 382608-10-8) and carbonic acid,cis-3-(2,5-dimethylphenyl)-8-methoxy-2-oxo-1-azaspiro[4.5]dec-3-en-4-ylethyl ester (CAS Reg. No.: 203313-25-1)]

17. Carboxamides

(for example flonicamid)

18. Octopaminergic agonists

(for example amitraz)

19. Inhibitors of magnesium-stimulated ATPase

(for example propargite)

20. Phthalamides

(for exampleN²-[1,1-dimethyl-2-(methylsulphonyl)ethyl]-3-iodo-N¹-[2-methyl-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-1,2-benzenedicarboxamide(CAS Reg. No.: 272451-65-7), flubendiamide)

21. Nereistoxin analogues

(for example thiocyclam hydrogen oxalate, thiosultap-sodium)

22. Biologicals, hormones or pheromones

(for example azadirachtin, Bacillus spec., Beauveria spec., codlemone,Metarrhizium spec., Paecilomyces spec., thuringiensin, Verticilliumspec.)

23. Active compounds with unknown or unspecific mechanisms of action

23.1 fumigants (for example aluminium phosphide, methyl bromide,sulphuryl fluoride)

23.2 selective antifeedants (for example cryolite, flonicamid,pymetrozine)

23.3 mite growth inhibitors (for example clofentezine, etoxazole,hexythiazox)

23.4 amidoflumet, benclothiaz, benzoximate, bifenazate, bromopropylate,buprofezin, chinomethionat, chlordimeform, chlorobenzilate,chloropicrin, clothiazoben, cycloprene, cyflumetofen, dicyclanil,fenoxacrim, fentrifanil, flubenzimine, flufenerim, flutenzin,gossyplure, hydramethylnone, japonilure, metoxadiazone, petroleum,piperonyl butoxide, potassium oleate, pyrafluprole, pyridalyl,pyriprole, sulfluramid, tetradifon, tetrasul, triarathene, verbutin,

and also the compound 3-methylphenyl propylcarbamate (tsumacide Z), thecompound3-(5-chloro-3-pyridinyl)-8-(2,2,2-trifluoroethyl)-8-azabicyclo[3.2.1]octane-3-carbonitrile(CAS Reg. No. 185982-80-3) and the corresponding 3-endo isomer (CAS Reg.No. 185984-60-5) (cf. WO 96/37494, WO 98/25923), and preparations whichcomprise insecticidally active plant extracts, nematodes, fungi orviruses.

Examples of suitable fungicide mixing partners may be selected in thefollowing list:

Inhibition of Nucleic Acid synthesis:

benalaxyl, benalaxyl-M, bupirimate, chiralaxyl, clozylacon,dimethirimol, ethirimol, furalaxyl, hymexazol, metalaxyl-M, ofurace,oxadixyl, oxolinic acid

Inhibition of Mitosis and Cell Division:

benomyl, carbendazim, diethofencarb, fuberidazole, pencycuron,thiabendazole thiophanate-methyl, zoxamide

Inhibition of Respiration.

CI: diflumetorim

CII boscalid, carboxin, fenfuram, flutolanil, furametpyr, mepronil,oxycarboxine, penthiopyrad, thifluzamide

CIII: azoxystrobin, cyazofamid, dimoxystrobin, enestrobin, famoxadone,fenamidone, fluoxastrobin, kresoxim-methyl, metominostrobin,orysastrobin, pyraclostrobin, picoxystrobin, trifloxystrobin,

Uncouplers: dinocap, fluazinam

Inhibition of ATP production: fentin acetate, fentin chloride, fentinhydroxide, silthiofam

Inhibition of AA and Protein Biosynthesis:

andoprim, blasticidin-S, cyprodinil, kasugamycin, kasugamycinhydrochloride hydrate, mepanipyrim, pyrimethanil,

Inhibition of Signal Transduction:

fenpiclonil, fludioxonil, quinoxyfen

Inhibition of Lipids and Membranes Synthesis:

chlozolinate, iprodione, procymidone, vinclozolin pyrazophos,edifenphos, iprobenfos (IBP), isoprothiolane tolclofos-methyl, biphenyliodocarb, propamocarb, propamocarb hydrochloride

Inhibition of Ergosterol Biosynthesis:

fenhexamid,

azaconazole, bitertanol, bromuconazole, cyproconazole, diclobutrazole,difenoconazole, diniconazole, diniconazole-M, epoxiconazole,etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol,furconazole, furconazole-cis, hexaconazole, imibenconazole, ipconazole,metconazole, myclobutanil, paclobutrazol, penconazole, propiconazole,prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon,triadimenol, triticonazole, uniconazole, voriconazole, imazalil,imazalil sulfate, oxpoconazole, fenarimol, flurprimidol, nuarimol,pyrifenox, triforine, pefurazoate, prochloraz, triflumizole,viniconazole,

aldimorph, dodemorph, dodemorph acetate, fenpropimorph, tridemorph,fenpropidin, spiroxamine

naftifine, pyributicarb, terbinafine,

Inhibition of Cell Wall Synthesis:

benthiavalicarb, bialaphos, dimethomorph, flumorph, iprovalicarb,polyoxins, polyoxorim, validamycin A

Inhibition of Melanine Biosynthesis:

carpropamid, diclocymet, fenoxanil, phtalide, pyroquilon, tricyclazole,

Host Defence Inducer:

acibenzolar-S-methyl, probenazole, tiadinil

Multisite:

captafol, captan, chlorothalonil, copper preparations such as: copperhydroxide, copper naphthenate, copper oxychloride, copper sulphate,copper oxide, oxine-copper and Bordeaux mixture, dichlofluanid,dithianon, dodine, dodine free base, ferbam, fluorofolpet, folpet,guazatine, guazatien acetate, iminoctadine, iminoctadine albesilate,iminoctadine triacetate, mancopper, mancozeb, maneb, metiram, metiramzinc, propineb, sulphur and sulphur preparations including calciumpolysulphide, thiram, tolylfluanid, zineb, ziram,

Unknown:

amibromdole, benthiazole, bethoxazin, capsimycin, carvone,chinomethionat, chloropicrin, cufraneb, cyflufenamid, cymoxanil,dazomet, debacarb, diclomezine, dichlorophen, dicloran, difenzoquat,difenzoquat methylsulphate, diphenylamine, ethaboxam, ferimzone,flumetover, flusulfamide, fosetyl-aluminium, fosetyl-calcium,fosetyl-sodium, fluopicolide, fluoroimide, hexachlorobenzene,8-hydroxyquinoline sulfate, irumamycin, methasulphocarb, metrafenone,methyl isothiocyanate, mildiomycin, natamycin, nickeldimethyldithiocarbamate, nitrothal-isopropyl, octhilinone, oxamocarb,oxyfenthiin, pentachlorophenol and salts, 2-phenylphenol and salts,phosphorous acid and its salts, piperalin, propanosine-sodium,proquinazid, pyrrolnitrine, quintozene, tecloftalam, tecnazene,triazoxide, trichlamide, zarilamid and2,3,5,6-tetrachloro-4-(methylsulfonyl)-pyridine,N-(4-Chloro-2-nitrophenyl)-N-ethyl-4-methyl-benzenesulfonamide,2-amino-4-methyl-N-phenyl-5-thiazolecarboxamide,2-chloro-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-3-pyridincarboxamide,3-[5-(4-chlorophenyl)-2,3-dimethylisoxazolidin-3-yl]pyridine,cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazole-1-yl)-cycloheptanol, methyl1-(2,3-dihydro-2,2-dimethyl-1H-inden-1-yl)-1H-imidazole-5-carboxylate,3,4,5-trichloro-2,6-pyridinedicarbonitrile, Methyl2-[[[cyclopropyl[(4-methoxyphenyl)imino]methyl]thio]methyl]-.alpha.-(methoxymethylene)-benzeneacetate,4-Chloro-alpha-propynyloxy-N-[2-[3-methoxy-4-(2-propynyloxy)phenyl]ethyl]-benzeneacetamide,(2S)-N-[2-[4-[[3-(4-chlorophenyl)-2-propynyl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(methylsulfonyl)amino]-butanamide,5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)[1,2,4]triazolo[1,5-a]pyrimidine,5-chloro-6-(2,4,6-trifluorophenyl)-N-[(1R)-1,2,2-trimethylpropyl][1,2,4]triazolo[1,5-a]pyrimidin-7-amine,5-chloro-N-[(1R)-1,2-dimethylpropyl]-6-(2,4,6-trifluorophenyl)[1,2,4]triazolo[1,5-a]pyrimidin-7-amine,N-[1-(5-bromo-3-chloropyridin-2-yl)ethyl]-2,4-dichloronicotinamide,N-(5-bromo-3-chloropyridin-2-yl)methyl-2,4-dichloronicotinamide,2-butoxy-6-iodo-3-propyl-benzopyranon-4-one,N-{(Z)-[(cyclopropylmethoxy)imino][6-(difluoromethoxy)-2,3-difluorophenyl]methyl}-2-phenylacetamide,N-(3-ethyl-3,5,5-trimethyl-cyclohexyl)-3-formylamino-2-hydroxy-benzamide,2-[[[[1-[3(1Fluoro-2-phenylethyl)oxy]phenyl]ethylidene]amino]oxy]methyl]-alpha-(methoxyimino)-N-methyl-alphaE-benzeneacetamide,N-{2-[3-chloro-5-(trifluoromethyl)pyridin-2-yl]ethyl}-2-(trifluoromethyl)benzamide,N-(3′,4′-dichloro-5-fluorobiphenyl-2-yl)-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide,1-[(4-methoxyphenoxy)methyl]-2,2-dimethylpropyl-1H-imidazole-1-carboxylicacid,O-[1-[(4-methoxyphenoxy)methyl]-2,2-dimethylpropyl]-1H-imidazole-1-carbothioicacid,2-(2-{[6-(3-chloro-2-methylphenoxy)-5-fluoropyrimidin-4-yl]oxy}phenyl)-2-(methoxyimino)-N-methylacetamide

The abovementioned components for combinations are known activesubstances, many of which are described in Ch. R Worthing, S. B. Walker,The Pesticide Manual, 13^(rd) Edition, British Crop Protection Council,Farnham 2003.

The effective use doses of the compounds employed in the invention canvary within wide limits, particularly depending on the nature of thepest to be eliminated or degree of infestation, for example, of cropswith these pests. In general, the compositions according to theinvention usually contain about 0.05 to about 95% (by weight) of one ormore active ingredients according to the invention, about 1 to about 95%of one or more solid or liquid carriers and, optionally, about 0.1 toabout 50% of one or more other compatible components, such assurface-active agents or the like.

In the present account, the term “carrier” denotes an organic orinorganic ingredient, natural or synthetic, with which the activeingredient is combined to facilitate its application, for example, tothe plant, to seeds or to the soil. This carrier is therefore generallyinert and it must be acceptable (for example, agronomically acceptable,particularly to the treated plant).

The carrier may be a solid, for example, clays, natural or syntheticsilicates, silica, resins, waxes, solid fertilizers (for exampleammonium salts), ground natural minerals, such as kaolins, clays, talc,chalk, quartz, attapulgite, montmorillonite, bentonite or diatomaceousearth, or ground synthetic minerals, such as silica, alumina, orsilicates especially aluminium or magnesium silicates. As solid carriersfor granules the following are suitable: crushed or fractionated naturalrocks such as calcite, marble, pumice, sepiolite and dolomite; syntheticgranules of inorganic or organic meals; granules of organic materialsuch as sawdust, coconut shells, corn cobs, corn husks or tobaccostalks; kieselguhr, tricalcium phosphate, powdered cork, or absorbentcarbon black; water soluble polymers, resins, waxes; or solidfertilizers. Such solid compositions may, if desired, contain one ormore compatible wetting, dispersing, emulsifying or colouring agentswhich, when solid, may also serve as a diluent.

The carrier may also be liquid, for example: water; alcohols,particularly butanol or glycol, as well as their ethers or esters,particularly methylglycol acetate; ketones, particularly acetone,cyclohexanone, methylethyl ketone, methylisobutylketone, or isophorone;petroleum fractions such as paraffinic or aromatic hydrocarbons,particularly xylenes or alkyl naphthalenes; mineral or vegetable oils;aliphatic chlorinated hydrocarbons, particularly trichloroethane ormethylene chloride; aromatic chlorinated hydrocarbons, particularlychlorobenzenes; water-soluble or strongly polar solvents such asdimethylformamide, dimethyl sulphoxide, or N-methylpyrrolidone;liquefied gases; or the like or a mixture thereof.

The surface-active agent may be an emulsifying agent, dispersing agentor wetting agent of the ionic or non-ionic type or a mixture of suchsurface-active agents. Amongst these are e.g., salts of polyacrylicacids, salts of lignosulphonic acids, salts of phenolsulphonic ornaphthalenesulphonic acids, polycondensates of ethylene oxide with fattyalcohols or fatty acids or fatty esters or fatty amines, substitutedphenols (particularly alkylphenols or arylphenols), salts ofsulphosuccinic acid esters, taurine derivatives (particularlyalkyltaurates), phosphoric esters of alcohols or of polycondensates ofethylene oxide with phenols, esters of fatty acids with polyols, orsulphate, sulphonate or phosphate functional derivatives of the abovecompounds. The presence of at least one surface-active agent isgenerally essential when the active ingredient and/or the inert carrierare only slightly water soluble or are not water soluble and the carrieragent of the composition for application is water.

Compositions of the invention may further contain other additives suchas adhesives or colorants. Adhesives such as carboxymethylcellulose ornatural or synthetic polymers in the form of powders, granules orlattices, such as arabic gum, polyvinyl alcohol or polyvinyl acetate,natural phospholipids, such as cephalins or lecithins, or syntheticphospholipids can be used in the formulations. It is possible to usecolorants such as inorganic pigments, for example: iron oxides, titaniumoxides or Prussian Blue; organic dyestuffs, such as alizarin dyestuffs,azo dyestuffs or metal phthalocyanine dyestuffs; or trace nutrients suchas salts of iron, manganese, boron, copper, cobalt, molybdenum or zinc.

For their agricultural application, the compounds of the invention aretherefore generally in the form of compositions, which are in varioussolid or liquid forms.

Solid forms of compositions which can be used are dusting powders (witha content of the compound of the invention, ranging up to 80%), wettablepowders or granules (including water dispersible granules), particularlythose obtained by extrusion, compacting, impregnation of a granularcarrier, or granulation starting from a powder (the content of thecompound of the invention, in these wettable powders or granules beingbetween about 0.5 and about 80%). Solid homogenous or heterogenouscompositions containing one or more compounds of the invention, forexample granules, pellets, briquettes or capsules, may be used to treatstanding or running water over a period of time. A similar effect may beachieved using trickle or intermittent feeds of water dispersibleconcentrates as described herein.

Liquid compositions, for example, include aqueous or non-aqueoussolutions or suspensions (such as emulsifiable concentrates, emulsions,flowables, dispersions, or solutions) or aerosols. Liquid compositionsalso include, in particular, emulsifiable concentrates, dispersions,emulsions, flowables, aerosols, wettable powders (or powder forspraying), dry flowables or pastes as forms of compositions which areliquid or intended to form liquid compositions when applied, for exampleas aqueous sprays (including low and ultra-low volume) or as fogs oraerosols.

Liquid compositions, for example, in the form of emulsifiable or solubleconcentrates most frequently comprise about 5 to about 80% by weight ofthe active ingredient, while the emulsions or solutions which are readyfor application contain, in their case, about 0.01 to about 20% of theactive ingredient. Besides the solvent, the emulsifiable or solubleconcentrates may contain, when required, about 2 to about 50% ofsuitable additives, such as stabilizers, surface-active agents,penetrating agents, corrosion inhibitors, colorants or adhesives.Emulsions of any required concentration, which are particularly suitablefor application, for example, to plants, may be obtained from theseconcentrates by dilution with water. These compositions are includedwithin the scope of the compositions which may be employed in thepresent invention. The emulsions may be in the form of water-in-oil oroil-in-water type and they may have a thick consistency.

The liquid compositions of this invention may, in addition to normalagricultural use applications be used for example to treat substrates orsites infested or liable to infestation by arthropods (or other pestscontrolled by compounds of this invention) including premises, outdooror indoor storage or processing areas, containers or equipment orstanding or running water.

All these aqueous dispersions or emulsions or spraying mixtures can beapplied, for example, to crops by any suitable means, chiefly byspraying, at rates which are generally of the order of about 100 toabout 1,200 liters of spraying mixture per hectare, but may be higher orlower (eg. low or ultra-low volume) depending upon the need orapplication technique. The compound or compositions according to theinvention are conveniently applied to vegetation and in particular toroots or leaves having pests to be eliminated. Another method ofapplication of the compounds or compositions according to the inventionis by chemigation, that is to say, the addition of a formulationcontaining the active ingredient to irrigation water. This irrigationmay be sprinkler irrigation for foliar pesticides or it can be groundirrigation or underground irrigation for soil or for systemicpesticides.

The concentrated suspensions, which can be applied by spraying, areprepared so as to produce a stable fluid product which does not settle(fine grinding) and usually contain from about 10 to about 75% by weightof active ingredient, from about 0.5 to about 30% of surface-activeagents, from about 0.1 to about 10% of thixotropic agents, from about 0to about 30% of suitable additives, such as anti-foaming agents,corrosion inhibitors, stabilizers, penetrating agents, adhesives and, asthe carrier, water or an organic liquid in which the active ingredientis poorly soluble or insoluble Some organic solids or inorganic saltsmay be dissolved in the carrier to help prevent settling or asantifreezes for water.

The wettable powers (or powder for spraying) are usually prepared sothat they contain from about 10 to about 80% by weight of activeingredient, from. about 20 to about 90% of a solid carrier, from about 0to about 5% of a wetting agent, from about 3 to about 10% of adispersing agent and, when necessary, from about 0 to about 80% of oneor more stabilizers and/or other additives, such as penetrating agents,adhesives, anti-caking agents, colorants, or the like. To obtain thesewettable powders, the active ingredient is thoroughly mixed in asuitable blender with additional substances which may be impregnated onthe porous filler and is ground using a mill or other suitable grinder.This produces wettable powders, the wettability and the suspendabilityof which are advantageous. They may be suspended in water to give anydesired concentration and this suspension can be employed veryadvantageously in particular for application to plant foliage.

The “water dispersible granules (WG)” (granules which are readilydispersible in water) have compositions which are substantially close tothat of the wettable powders. They may be prepared by granulation offormulations described for the wettable powders, either by a wet route(contacting finely divided active ingredient with the inert filler and alittle water, e.g. 1 to 20% by weight, or with an aqueous solution of adispersing agent or binder, followed by drying and screening), or by adry route (compacting followed by grinding and screening).

The rates and concentrations of the formulated compositions may varyaccording to the method of application or the nature of the compositionsor use thereof.

Generally speaking, the compositions for application to controlarthropod or plant nematode pests usually contain from about 0.00001% toabout 95%, more particularly from about 0.0005% to about 50% by weightof one or more compounds of the invention, or of total activeingredients (that is to say the compounds of the invention, togetherwith other substances toxic to arthropods or plant nematodes,synergists, trace elements or stabilizers). The actual compositionsemployed and their rate of application will be selected to achieve thedesired effect(s) by the farmer, livestock producer, medical orveterinary practitioner, pest control operator or other person skilledin the art.

Solid or liquid compositions for application topically to animals,timber, stored products or household goods usually contain from about0.00005% to about 90%, more particularly from about 0.001% to about 10%,by weight of one or more compounds of the invention. For administrationto animals orally or parenterally, including percutaneously solid orliquid compositions, these normally contain from about 0.1% to about 90%by weight of one or more compounds of the invention.

Medicated feedstuffs normally contain from about 0.001% to about 3% byweight of one or more compounds of the invention. Concentrates orsupplements for mixing with feedstuffs normally contain from about 5% toabout 90%, preferably from about 5% to about 50%, by weight of one ormore compounds of the invention. Mineral salt licks normally containfrom about 0 1% to about 10% by weight of one or more compounds offormula (I) or pesticidally acceptable salts thereof.

Dusts or liquid compositions for application to livestock, goods,premises or outdoor areas may contain from about 0.0001% to about 15%,more especially from about 0.005% to about 2.0%, by weight, of one ormore compounds of the invention. Suitable concentrations in treatedwaters are between about 0.0001 ppm and about 20 ppm, more particularlyabout 0.001 ppm to about 5.0 ppm. of one or more compounds of theinvention, and may be used therapeutically in fish farming withappropriate exposure times. Edible baits may contain from about 0.01% toabout 5%, preferably from about 0.01% to about 1.0%, by weight, of oneor more compounds of the invention.

When administered to vertebrates parenterally, orally or by percutaneousor other means, the dosage of compounds of the invention, will dependupon the species, age, or health of the vertebrate and upon the natureand degree of its actual or potential infestation by arthropod orhelminth pests. A single dose of about 0.1 to about 100 mg, preferablyabout 2.0 to about 20.0 mg, per kg body weight of the animal or doses ofabout 0.01 to about 20.0 mg, preferably about 0.1 to about 5.0 mg, perkg body weight of the animal per day, for sustained medication, aregenerally suitable by oral or parenteral administration. By use ofsustained release formulations or devices, the daily doses required overa period of months may be combined and administered to animals on asingle occasion.

The following composition EXAMPLES 2A-2M illustrate compositions for useagainst arthropods, especially mites or insects, or plant nematodes,which comprise, as active ingredient, compounds of the invention, suchas those described in preparative examples. The compositions describedin EXAMPLES 2A-2M can each be diluted to give a sprayable compositon atconcentrations suitable for use in the field. Generic chemicaldescriptions of the ingredients (for which all of the followingpercentages are in weight percent), used in the composition EXAMPLES2A-2M exemplified below, are as follows: Trade Name Chemical DescriptionEthylan BCP Nonylphenol ethylene oxide condensate Soprophor BSUTristyrylphenol ethylene oxide condensate Arylan CA A 70% w/v solutionof calcium dodecylbenzenesulfonate Solvesso 150 Light C₁₀ aromaticsolvent Arylan S Sodium dodecylbenzenesulfonate Darvan NO₂ Sodiumlignosulphonate Celite PF Synthetic magnesium silicate carrier SoproponT36 Sodium salts of polycarboxylic acids Rhodigel 23 Polysaccharidexanthan gum Bentone 38 Organic derivative of magnesium montmorilloniteAerosil Microfine silicon dioxide

Example 2A

A water soluble concentrate is prepared with the composition as follows:Active ingredient  7% Ethylan BCP 10% N-methylpyrrolidone 83%

To a solution of Ethylan BCP dissolved in a portion ofN-methylpyrrolidone is added the active ingredient with heating andstirring until dissolved. The resulting solution is made up to volumewith the remainder of the solvent.

Example 2B

An emulsifiable concentrate (EC) is prepared with the composition asfollows: Active ingredient 25%(max) Soprophor BSU 10% Arylan CA  5%N-methylpyrrolidone 50% Solvesso 150 10%

The first three components are dissolved in N-methylpyrrolidone and tothis is then added the Solvesso 150 to give the final volume.

Example 2C

A wettable powder (WP) is prepared with the composition as follows:Active ingredient 40% Arylan S  2% Darvan NO₂  5% Celite PF 53%

The ingredients are mixed and ground in a hammer-mill to a powder with aparticle size of less than 50 microns.

Example 2D

An aqueous-flowable formulation is prepared with the composition asfollows: Active ingredient 40.00% Ethylan BCP 1.00% Sopropon T360. 0.20%Ethylene glycol 5.00% Rhodigel 230. 0.15% Water 53.65%

The ingredients are intimately mixed and are ground in a bead mill untila mean particle size of less than 3 microns is obtained.

Example 2E

An emulsifiable suspension concentrate is prepared with the compositionas follows: Active ingredient 30.0% Ethylan BCP 10.0% Bentone 38 0.5%Solvesso 150 59.5%

The ingredients are intimately mixed and ground in a beadmill until amean particle size of less than 3 microns is obtained.

Example 2F

A water dispersible granule is prepared with the composition as follows:Active ingredient 30% Darvan No 2 15% Arylan S  8% Celite PF 47%

The ingredients are mixed, micronized in a fluid-energy mill and thengranulated in a rotating pelletizer by spraying with water (up to 10%).The resulting granules are dried in a fluid-bed drier to remove excesswater.

Example 2G

A dusting powder is prepared with the composition as follows: Activeingredient  1 to 10% Talc powder-superfine 99 to 90%

The ingredients are intimately mixed and further ground as necessary toachieve a fine powder. This powder may be applied to a locus ofarthropod infestation, for example refuse dumps, stored products orhousehold goods or animals infested by, or at risk of infestation by,arthropods to control the arthropods by oral ingestion. Suitable meansfor distributing the dusting powder to the locus of arthropodinfestation include mechanical blowers, handshakers or livestock selftreatment devices.

Example 2H

An edible bait is prepared with the composition as follows: Activeingredient   0.1 to 1.0% Wheat flour 80% Molasses 19.9 to 19%

The ingredients are intimately mixed and formed as required into a baitform. This edible bait may be distributed at a locus, for exampledomestic or industrial premises, e.g. kitchens, hospitals or stores, oroutdoor areas, infested by arthropods, for example ants, locusts,cockroaches or flies, to control the arthropods by oral ingestion.

Example 2I

A solution formulation is prepared with a composition as follows: Activeingredient 15% Dimethyl sulfoxide 85%

The active ingredient is dissolved in dimethyl sulfoxide with mixing andor heating as required. This solution may be applied percutaneously as apour-on application to domestic animals infested by arthropods or, aftersterilization by filtration through a polytetrafluoroethylene membrane(0.22 micrometer pore size), by parenteral injection, at a rate ofapplication of from 1.2 to 12 ml of solution per 100 kg of animal bodyweight.

Example 2J

A wettable powder is prepared with the composition as follows: Activeingredient 50% Ethylan BCP  5% Aerosil  5% Celite PF 40%

The Ethylan BCP is absorbed onto the Aerosil which is then mixed withthe other ingredients and ground in a hammer-mill to give a wettablepowder, which may be diluted with water to a concentration of from0.001% to 2% by weight of the active compound and applied to a locus ofinfestation by arthropods, for example, dipterous larvae or plantnematodes, by spraying, or to domestic animals infested by, or at riskof infection by arthropods, by spraying or dipping, or by oraladministration in drinking water, to control the arthropods.

Example 2K

A slow release bolus composition is formed from granules containing thefollowing components in varying percentages(similar to those describedfor the previous compositions) depending upon need:

-   -   Active ingredient    -   Density agent    -   Slow-release agent    -   Binder

The intimately mixed ingredients are formed into granules which arecompressed into a bolus with a specific gravity of 2 or more. This canbe administered orally to ruminant domestic animals for retention withinthe reticulo-rumen to give a continual slow release of active compoundover an extended period of time to control infestation of the ruminantdomestic animals by arthropods.

Example 2L

A slow release composition in the form of granules, pellets, brickettesor the like can be prepared with compositions as follows:

-   -   Active ingredient 0.5 to 25%    -   Polyvinyl chloride 75 to 99.5%    -   Dioctyl phthalate (plasticizer)

The components are blended and then formed into suitable shapes bymelt-extrusion or molding. These composition are useful, for example,for addition to standing water or for fabrication into collars oreartags for attachment to domestic animals to control pests by slowrelease.

Example 2M

A water dispersible granule is prepared with the composition as follows:Active ingredient 85%(max) Polyvinylpyrrolidone 5% Attapulgite clay 6%Sodium lauryl sulfate 2% Glycerine 2%

The ingredients are mixed as a 45% slurry with water and wet milled to aparticle size of 4 microns, then spray-dried to remove water.

Methods of Pesticidal Use

-   -   The following representative test procedure, using compounds of        the invention, was conducted to determine the parasiticidal        activity of compounds of the invention.

METHOD A: Screening method to test systemicity of compounds againstCtenocephalides felis (Cat flea)

A test container was filled with 10 adults of Ctenocephalides felis. Aglass cylinder was closed on one end with parafilm and placed on top ofthe test container. The test compound solution was then pipetted intobovine blood and added to the glass cylinder. The treatedCtenocephalides felis l were held in this artificial dog test (blood 37°C., 40-60% relative humidity; Ctenocephalides felis 20-22° C., 40-60%relative humidity) and assessment performed at 24 and 48 hours afterapplication.

Compound numbers 1.4, 1.5 and 1.6 gave at least 90% control ofCtenocephalides felis at a test concentration of 5 ppm or less.

1. A compound of formula (I):

wherein: Q is CN or CSNH₂; R¹ is CN, CF₃ or CSNH₂; R² is (C₁-C₃)-alkylor (C₁-C₃)-haloalkyl; R³ is (C₃-C₆)-alkenyl, (C₃-C₆)-alkynyl, R⁶,(C₃-C₆)-cycloalkyl or (C₁-C₄)-alkyl which last mentioned group isunsubstituted or substituted by one or more radicals selected from thegroup consisting of halogen, (C₁-C₄)-alkoxy, S(O)_(m)R⁷, R⁶,(C₃-C₆)-cycloalkyl, CO₂(CH₂)_(q)R⁶, CO₂(CH₂)_(q)R^(6a) and CO₂R⁷; R⁴ is(C₂-C₄)-alkyl or (C₂-C₄)-haloalkyl which groups are unsubstituted orsubstituted by a radical selected from the group consisting of NHCOR⁸,NHR⁸, NR⁸COR⁸, OCOR⁴, OR⁶, OR^(6a), S(O)_(p)(CH₂)_(q)R⁶,S(O)_(p)(CH₂)_(q)R^(6a), ═N—R⁸, ═NNHR⁸, ═NOR⁸, ═NOH, ═NNHC(═X)R⁸,═NNHC(═X)NH₂, NNR⁸C(═X)NH₂, NNHC(═O)O(CH₂)_(q)R⁹, (C₁-C₄)-alkoxy andS(O)_(m)R⁷ (wherein two (C₁-C₄)-alkoxy or S(O)_(m)R⁷ radicals may beattached to the same carbon atom to form an acetal, thioacetal orhemithioacetat group or a cyclic acetal, thioacetal or hemithioacetalwhich contains 5 or 6 ring atoms); or is CO₂R⁹, COCOR¹⁰, SO₂R⁸, COR⁸,COCH₂OR⁸ or P(═X)(—YR⁸)(-ZR^(8a)); R⁵ is CF₃, OCF₃, SF₆ or halogen; W isC-halogen, C—NR¹¹R¹² or N; X is O or S; Y and Z are each independentlyO, S or a covalent bond; R⁶ is phenyl unsubstituted or substituted byone or more radicals selected from the group consisting of halogen,(C₁-C₄)-alkyl, (C₁-C₄)haloalkyl, (C₁-C₄)-alkoxy, (C₁-C₄)-haloalkoxy, CN,NO₂, S(O)_(p)R⁷ and NR¹¹R¹²; R^(6a) is heteroaryl unsubstituted orsubstituted by one or more radicals selected from the group consistingof halogen, (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl, (C₁-C₄)-alkoxy,(C₁-C₄)-haloalkoxy, CN, NO₂, S(O)_(p)R⁷, NR¹¹R¹², OH and oxo; R⁷ is(C₁-C₄)-alkyl or (C₁-C₄)-haloalkyl; R⁸ and R^(8a) are each independently(C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl, (C₃-C₆)-cycloalkyl-(C₁-C₃)-alkyl or(CH₂)_(q)R⁶; R⁹ is R⁶, (C₃-C₄)-alkynyl or (C₁-C₄)-alkyl or (C₁-C₄)-alkylwhich last mentioned group is unsubstituted or substituted by one ormore radicals selected from the group consisting of halogen(C₁-C₄)-alkoxy, (C₁-C₄)haloalkoxy, R⁶, S(O)_(m)R⁶ and(C₃-C₅)-cycloalkyl; R¹⁰ is OR⁹ or NR¹³R¹⁴; R¹¹ and R¹² are eachindependently H, (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl, (C₃-C₄)-alkenyl,(C₃-C₄)-haloalkenyl, (C₃-C₄)-alkynyl, (C₃-C₆)-cycloalkyl or(C₃-C₆)-cycloalkyl-(C₁-C₄)-alkyl; or R¹¹ and R¹² together with theattache N atom form a five- or six-membered saturated or unsaturatedring which optionally contains an additional hetro atom in the ringwhich is selected from O, S and N, the ring being unsubstituted orsubstituted by one or more radicals selected from the group consistingof halogen, (C₁-C₄)-alkyl and (C₁-C₄)-haloalkyl; R¹³ is H, (C₁-C₄)-alkylor R⁶; R¹⁴ is H or R⁹; m, n and p are each independently 0, 1 or 2; q is0 or 1; and each heteroaryl in the above-mentioned radicals isindependently a heteroaromatic radical having 3 to 7 ring atoms and 1, 2or 3 hetero atoms in the ring selected from the group consisting of N, Oand S; or a pesticidally acceptable salt thereof.
 2. A compound or asalt thereof as claimed in claim 1 wherein Q and R¹ are each CN.
 3. Acompound or a salt thereof as claimed in claim 1 wherein R² and R⁵ areeach CF₃.
 4. A compound or a salt thereof as claimed in claim 1 whereinQ and R¹ are each CN; R² and R⁵ are each CF₃; W is C—Cl; and the otherradicals are as defined in claim
 1. 5. A compound or a salt thereof asclaimed in claim 1 wherein Q and R¹ are each CN; R² is (C₂-C₄)-alkyl or(C₂-C₄)-haloalkyl which groups are substituted by a radical selectedfrom the group consisting of NHCOR⁸, NHR⁸, NR⁸COR⁸, OCOR⁸, OR⁶, OR^(6a),S(O)_(p)(CH₂)_(q)R⁶, S(O)_(p)(CH₂)_(q)R^(6a), ═N—R⁸, ═NNHR⁸, ═NOR⁸,═NOH, ═NNHC(═X)R⁸, ═NNHC(═X)NH₂, NNR⁸C(═X)NH₂, NNR⁸C(═X)NH₂,═NNHC(═O)O(CH₂)_(q)R⁹, (C₁-C₄)-alkoxy and S(O)_(m)R⁷ (wherein two(C₁-C₄)-alkoxy or S(O)_(m)R⁷ radicals may be attached to the same carbonatom to form an acetal, thioacetal or hemithioacetal group or a cyclicacetal, thioacetal or hemithioacetal which contains 5 or 6 ring atoms);or is CO₂R⁹, COCOR¹⁰, SO₂R⁸, COR⁸, COCH₂OR₈ or P(═X)(—YR⁸)(-ZR^(8a)); R⁵is CF₃; W is C—Cl; and the other radicals are as define in claim
 1. 6. Aprocess for the preparation of a compound of formula (I) or a saltthereof as defined in claim 1, which process comprises: a) where Q isCN, R¹ is CN or CF₃, and R², R³, R⁴, R⁵, W and n are as defined in claim1, reacting a corresponding compound of Formula (II):

wherein the various values are as defined in claim 1, with a compound offormula (III):R⁴-L   (III) wherein R⁴ is as defined in claim 1, and L is a leavinggroup; or b) where Q is CN, R¹ is ON or CF₃, and R², R³, R⁴, R⁵, W and nare as defined in claim 1, reacting a compound of formula (IV):

wherein L¹ is a leaving group, and the other values are as defined inclaim 1, with a compound of formula (V):R³R⁴N—H   (V) wherein R³ and R⁴ are as defined in claim 1, in thepresence of a base; or c) where R⁴ is (C₂-C₄)-alkyl or (C₂-C₄)-haloalkylwhich groups are substituted by a radical selected from the groupconsisting of ═N—R⁸, ═NNHR⁸, ═NOR⁸, ═NOH, ═NNHC(═X)R⁸, ═NNHC(═X)NH₂,NNR⁸C(═X)NH₂ and ═NNHC(═O)O(CH₂)_(q)R⁹, Q is CN, R¹ is CN or CF₃, andR², R³, R⁵, W and n are as defined in claim 1, reacting a correspondingcompound of formula (I) in which the (C₂-C₄)-alkyl carbon atom bearingthe relevant radical is replaced by a carbon atom substituted by acarbonyl group or an acetal derivative thereof, with a compound offormula (VI), (VII) (VIII), (IX), (X) (XI), (XII) or (XIII):NH₂—R   (VI)NH₂NHR⁸   (VII)NH₂OR⁸   (VIII)NH₂OH   (IX)NH₂NHC(═X)R⁸   (X)NH₂NHC(═X)NH₂   (XI)NH₂NR⁸C(═X)NH₂   (XII)NH₂NHC(═O)O(CH₂)_(q)R⁹   (XIII) wherein the various values are asdefined in claim 1, or an acid salt thereof, in the presence of a strongacid; or d) where Q and/or R¹ is CSNH₂, and the other values are asdefined in claim 1, reacting the corresponding compound of formula (I)wherein Q and/or R¹ is CN, with an alkali or alkaline earth metalhydrosulfide, or with H₂S in the presence of an organic base, or withthe reagent Ph₂PS₂; or e) where Q, and/or R¹ is CSNH₂, and the othervalues are as defined in claim 1, reacting the corresponding compound offormula (I) wherein Q and/or R¹ is ON, with a bis(trialkylsilyl)sulfide,in the presence of a base; or f) where n is 1 or 2 and R¹, R², R³, R⁴,R⁵ and W are as defined in claim 1, oxidising the corresponding compoundin which n is 0 or 1; and g) if desired, conversing a resulting compoundof formula (I) in a pesticidally acceptable salt thereof.
 7. Apesticidal composition comprising a compound of formula (1) or apesticidally acceptable salt thereof as defined in claim 1, inassociation with a pesticidally acceptable diluent or carrier and/orsurface active agent.
 8. The use of a compound of formula (1) or a saltthereof according to claim 1, for the preparation of a veterinarymedicament.
 9. The use of a compound of formula (1) or a salt thereofaccording to claim 1, for the control of pests.
 10. A method forcontrolling pests at a locus which comprises applying thereto aneffective amount of a compound of formula (1) or a salt thereof asclaimed in claim
 1. 11. A compound of formula (XVIII):

wherein n is 0, 1 or 2.